TW201807138A - Adhesive film to be used in multilayer printed circuit board - Google Patents

Abstract

An adhesive film to be used in a multilayer printed circuit board and having a resin composition layer obtained by forming a layer, on a support film, of a resin composition that contains: (a) a novolac phenolic resin in which the dispersity (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.05-1.8; (b) an epoxy resin represented by general formula (1); and (c) an inorganic filler material. Therein, the average particle diameter of the (c) inorganic filler material in the resin composition layer is 0.1[mu]m or higher, and the content of the inorganic filler material constitutes 20-95 mass% of the solid content of the resin.

Description

Adhesive film for multilayer printed wiring board

The present invention relates to an adhesive film for a multilayer printed wiring board.

In recent years, in multilayer printed wiring boards used in electronic equipment, communication equipment, and the like, not only has miniaturization, weight reduction, and high-density wiring been achieved, but also demands for high-speed calculation processing have increased. Accordingly, as a method for manufacturing a multilayer printed wiring board, a build-up manufacturing technique in which interlayer insulating layers are alternately stacked on a wiring layer of a circuit board has attracted attention.

In the manufacturing method of the add-on method, as a method of manufacturing the interlayer insulating layer and the wiring layer, a method of forming a wiring using a so-called "color reduction method" is generally used. The "color reduction method" uses a pressure device and uses A resin composition for forming an interlayer insulating layer (hereinafter, also referred to as a "resin composition for an interlayer insulating layer") and a copper foil used to form a wiring layer are pressurized at a high temperature for a long time to make the resin for the interlayer insulating layer After the composition is thermally cured to obtain an interlayer insulating layer having a copper foil, a via hole for an interlayer connection is formed by using a drilling method, a laser method, or the like as necessary. Then, a necessary portion is left and the copper foil is removed by etching. .

In addition, with the above-mentioned requirements for miniaturization, weight reduction, and high-density wiring of multilayer printed wiring boards, the so-called "addition method" has attracted attention. The "addition method" uses a vacuum laminator. After the resin composition for the interlayer insulation layer and the copper foil are pressed at high temperature for a short time, the resin composition for the interlayer insulation layer is thermally hardened at a high temperature using a dryer or the like, and a drilling method or a laser method is used if necessary. The vias for interlayer connection are formed by waiting, and a wiring layer is formed on a necessary portion by a plating method.

The resin composition for the interlayer insulation layer used in the extension method mainly uses an aromatic epoxy resin and a hardener having an active hydrogen for the epoxy resin (for example, a phenol-based hardener, an amine-based hardener, and a carboxylic acid). Acid hardener, etc.). Although the hardened material obtained by hardening using these hardeners has excellent physical property balance, a highly polar hydroxyl group is generated by the reaction of the epoxy group and the active hydrogen of the hardener, which leads to an increase in water absorption and relative dielectric properties. The problem of degradation of electrical characteristics such as constant and dielectric loss tangent. Moreover, when using these hardening | curing agents, there exists a problem that the storage stability of a resin composition is impaired.

On the other hand, it is known that a cyanate resin having a thermosetting curable cyanate group provides a cured product excellent in electrical characteristics. However, the reaction of the cyano group to form an S-triazine ring by thermal curing requires, for example, 230 ° C and 120 minutes or more of high temperature and relatively long-term hardening. The resin composition for an interlayer insulating layer is not suitable. As a method for reducing the curing temperature of a cyanate resin, a method is known in which a cyanate resin and an epoxy resin are used in combination and a hardening catalyst is used to harden them (for example, refer to Patent Documents 1 and 2).

In addition, for the additional layer, in order to reduce the dimensional stability of the process and reduce the amount of warpage after semiconductor mounting, a low thermal expansion coefficient (low CTE (Coefficient Of Thermal Expansion)) is required, and a group suitable for low CTE is required. (For example, refer to Patent Documents 3 to 5). As the most mainstream method, a low CTE of the build-up layer is often achieved by increasing the filling of the silica fill (for example, setting 40% by mass or more of the build-up layer as the silica fill). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-40298 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2010-90237 [Patent Literature 3] Japanese Patent Publication No. 2006-527920 [Patent Literature 4] Japanese Patent Special JP 2007-87982 [Patent Document 5] Japanese Patent Laid-Open No. 2009-280758

[Problems to be Solved by the Invention] [1] If the silicon dioxide filler is highly filled in order to reduce the CTE of the additional layer, there is a problem that it is difficult to embed the wiring pattern of the inner layer circuit by the additional material. Tendency in bumps. In addition, it is required to embed an inner layer circuit such as a through-hole with a build-up material so that the unevenness becomes smaller. If the silica filler is highly filled in order to reduce the CTE of a building material, it tends to be difficult to satisfy these requirements.

The first invention was made to solve the above-mentioned problem, and an object thereof is to provide an adhesive film for a multilayer printed wiring board that is excellent in embedding unevenness even when a silicon dioxide filler is highly filled.

[2] As described above, when a cyanate resin and an epoxy resin are used in combination, the curing temperature can be reduced, and on the other hand, the storage stability as a resin composition tends to be reduced. With the decrease in storage stability, when this resin composition is stored or used as a resin film for an interlayer insulating layer, there are cases where operability problems such as film cracking may occur. In particular, in the case where the inorganic filler is highly filled for the purpose of lowering CTE and improving electrical characteristics, since film breakage is more likely to occur, storage stability and operation as a resin film for an interlayer insulating layer are expected. Sexual improvement.

The second invention is made in order to solve the above-mentioned problems, and an object thereof is to provide a resin film for an interlayer insulating layer which can obtain an interlayer insulating layer having excellent electrical characteristics and heat resistance, and which is excellent in storage stability and handling properties. A multilayer resin film of a resin film for an interlayer insulating layer and a multilayer printed wiring board. [Means for solving problems]

[1] The present inventors have made intensive studies in order to solve the above-mentioned first problem, and as a result, have found that by using a resin composition containing a specific novolak-type phenol resin, a specific epoxy resin, and a specific inorganic filler Object, the first problem can be solved, and the present invention has been completed. That is, the first invention provides the following adhesive film.

An adhesive film for a multilayer printed wiring board comprises a resin composition layer formed by forming a layer of the following resin composition on a support film, the resin composition comprising: (a) a novolac phenol resin, The dispersion ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.05 to 1.8; (b) an epoxy resin represented by the following general formula (I); and (c) an inorganic filler And (c) the average particle diameter of the inorganic filler in the resin composition layer is 0.1 μm or more, and the content of the (c) inorganic filler is 20% to 95% by mass of the resin solid content.

[Chemical 1] (Where p is an integer from 1 to 5)

[2] The present inventors have made repeated efforts to solve the second problem, and found that the problem can be solved by the following invention. That is, the second invention provides the following (1) to (18). (1) A resin film for an interlayer insulating layer, which is composed of a thermosetting resin containing (A) an epoxy resin, (B) a cyanate resin, (C) an inorganic filler, and (D) a monofunctional phenol compound. The content of (C) the inorganic filler is 50 to 85 parts by mass based on 100 parts by mass of the solid content of the thermosetting resin composition. (2) The resin film for an interlayer insulating layer according to the above (1), wherein the (D) monofunctional phenol compound in the thermosetting resin composition is (100) parts by mass with respect to (B) a cyanate resin. The content is 0.5 to 35 parts by mass. (3) The resin film for an interlayer insulating layer according to (1) or (2), wherein the volume average particle diameter of the (C) inorganic filler is 0.01 μm to 5 μm. (4) The resin film for an interlayer insulating layer according to any one of (1) to (3), wherein the thermosetting resin composition further contains (E) a phenoxy resin. (5) The resin film for an interlayer insulating layer according to the above (4), wherein the (E) phenoxy resin contains an alicyclic structure. (6) The resin film for an interlayer insulating layer according to the above (4) or (5), wherein the thermosetting resin composition contains 100 parts by mass of a solid content of the thermosetting resin composition, The content of the (E) phenoxy resin is 0.2 to 10 parts by mass. (7) The resin film for an interlayer insulating layer according to any one of (1) to (6), wherein the thermosetting resin composition further contains (F) an active ester curing agent. (8) The resin film for an interlayer insulating layer according to the above (7), wherein the active ester group derived from the (F) active ester hardener and the (A) ring are contained in the thermosetting resin composition. The epoxy resin has an epoxy group equivalent ratio (active ester group / epoxy group) of 0.1 to 0.7. (9) A multilayer resin film comprising a resin composition layer for an interlayer insulating layer including the resin film for an interlayer insulating layer according to any one of (1) to (8), and an adhesive auxiliary layer. (10) The multilayer resin film according to the above (9), wherein the adhesion auxiliary layer is formed using a resin composition for an adhesion auxiliary layer. (11) The multilayer resin film according to the above (10), wherein the resin composition for an auxiliary layer contains (H) a cyanate resin. (12) The multilayer resin film according to the above (10) or (11), wherein the resin composition for an auxiliary layer further contains (J) an epoxy resin. (13) The multilayer resin film according to any one of (10) to (12), wherein the resin composition for an auxiliary layer further contains (K) selected from the group consisting of a polyimide resin and a polyimide At least one of the group consisting of a resin and a polybenzoxazole resin. (14) The multilayer resin film according to the above (13), wherein the resin composition for an auxiliary layer contains a polyamide resin as the component (K), and the polyamide resin contains a phenolic hydroxyl group. (15) The multilayer resin film according to any one of (10) to (14), wherein the resin composition for an auxiliary layer further contains (L) a specific surface area of 20 m ² / g to 500 m ² / g of inorganic filler. (16) The multilayer resin film according to the above (15), wherein the specific surface area (L) is 20 m ² / g to 500 m ² / g with respect to 100 parts by mass of the solid content of the resin composition for the auxiliary layer. The content of the inorganic filler is 3 to 40 parts by mass. (17) A multilayer printed wiring board using a resin film selected from the resin film for an interlayer insulating layer according to any one of the above (1) to (8) and any one of the above (9) to (16) One or more types of the group consisting of the multilayer resin film as described in this item. (18) A semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board according to the above (17). [Effect of the invention]

[1] According to the first invention, even if a silicon dioxide filler is highly filled, an adhesive film for a multilayer printed wiring board that is excellent in embedding unevenness can be provided.

[2] According to the second invention, it is possible to provide a resin film for an interlayer insulating layer which can obtain an interlayer insulating layer having excellent electrical characteristics and heat resistance and excellent storage stability and handling properties, and use the resin film for an interlayer insulating layer. Multilayer resin film and multilayer printed wiring board.

[1] First invention The adhesive film for a multilayer printed wiring board of the present invention includes a resin obtained by forming a layer of the following resin composition (hereinafter, also referred to as a "resin composition for adhesive film") on a support film. A composition layer, wherein the resin composition includes: (a) a novolac phenol resin (hereinafter, also referred to simply as a abbreviation for a weight average molecular weight (Mw) and a number average molecular weight (Mn) dispersion ratio (Mw / Mn) of 1.05 to 1.8 "(A) novolac-type phenol resin"), (b) an epoxy resin represented by the general formula (I) (hereinafter, also simply referred to as "(A) epoxy resin"), and (c) inorganic The filler has an average particle diameter of (c) the inorganic filler in the resin composition layer of 0.1 μm or more, and the content of the (c) inorganic filler is 20% to 95% by mass of the resin solid content.

[Resin composition for subsequent film] The resin composition for the subsequent film includes (a) a novolac phenol resin, (A) an epoxy resin, and (c) an inorganic filler. Each of these components will be described below.

<(A) Novolac phenol resin> (a) Novolac phenol resin is used as a hardener for epoxy resin, and the dispersion ratio (Mw / Mn) of its weight average molecular weight (Mw) and number average molecular weight (Mn) is The range is 1.05 to 1.8.

The (a) novolak-type phenol resin as described above can be produced, for example, by the production method described in Japanese Patent No. 4,283,783. That is, using a phenol compound and an aldehyde compound as raw materials, a phosphoric acid compound as an acid catalyst, and a non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent, the two-layer separation state formed by these is, for example, mechanically stirred, It is agitated and mixed by ultrasonic waves, and becomes a two-layer (organic phase and water phase) mixed turbid heterogeneous reaction system (phase separation reaction). The reaction of a phenol compound and an aldehyde compound proceeds to synthesize a condensate (resin). Next, for example, a water-insoluble organic solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, etc.) is added and mixed, the condensate is dissolved, the stirring is stopped, and the mixture is allowed to stand and separated into an organic phase ( (Organic solvent phase) and water phase (phosphoric acid aqueous solution phase), the water phase is removed for recovery, on the other hand, the organic phase is washed with hot water and / or neutralized, and then the organic solvent is distilled and recovered, thereby manufacturing (a ) Novolac phenol resin. Since the method for producing a novolac phenol resin uses a phase separation reaction, the stirring efficiency is extremely important. From the aspect of reaction efficiency, it is desirable to miniaturize the two phases in the reaction system so as to increase the surface area of the interface as much as possible. This promotes the conversion of phenolic compounds to resins.

Examples of the phenol compound used as a raw material include phenol, o-cresol, m-cresol, p-cresol, xylenol, and bisphenol compound. The ortho position has 3 or more carbon atoms, and preferably 3 to 10 carbon atoms. The ortho-substituted phenol compound of the hydrocarbyl group is a para-substituted phenol compound having a hydrocarbon group of 3 or more, preferably 3 to 18 carbon atoms in the para position. These compounds can be used alone or in combination of two or more. Examples of the bisphenol compound include bisphenol A, bisphenol F, bis (2-methylphenol) A, bis (2-methylphenol) F, bisphenol S, bisphenol E, and bisphenol Z. . Examples of ortho-substituted phenol compounds include 2-propylphenol, 2-isopropylphenol, 2-second butylphenol, 2-third butylphenol, 2-phenylphenol, 2-cyclohexylphenol, 2-nonylphenol, 2-naphthylphenol, and the like. Examples of the para-substituted phenol compound include 4-propylphenol, 4-isopropylphenol, 4-second butylphenol, 4-thirdbutylphenol, 4-phenylphenol, 4-cyclohexylphenol, 4-nonylphenol, 4-naphthylphenol, 4-dodecylphenol, 4-octadecylphenol, and the like.

Examples of the aldehyde compound used as a raw material include formaldehyde, formalin, p-formaldehyde, trioxane, acetaldehyde, paraldehyde, and propionaldehyde. Among these compounds, paraformaldehyde is preferred from the viewpoint of the reaction rate. These compounds can be used alone or in combination of two or more.

The blending molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P) is preferably 0.33 or more, more preferably 0.40 to 1.0, and even more preferably 0.50 to 0.90. By setting the blending molar ratio (F / P) within the range, excellent yield can be obtained.

The phosphoric acid compound used as an acid catalyst plays an important role in that it forms a place for a phase separation reaction with a phenol compound in the presence of water. As the phosphoric acid compound, for example, an aqueous solution type of 89% by mass phosphoric acid or 75% by mass phosphoric acid can be used. Moreover, if necessary, polyphosphoric acid, phosphoric anhydride, etc. can also be used. From the viewpoint of controlling the phase separation effect, for example, the content of the phosphoric acid compound is 5 parts by mass or more, preferably 25 parts by mass or more, and more preferably 50 parts by mass to 100 parts by mass based on 100 parts by mass of the phenol compound. When 70 parts by mass or more of the phosphoric acid compound is used, it is preferable to suppress the heat generation at the initial stage of the reaction by ensuring the safety by introducing the batch into the reaction system.

The non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent plays an extremely important role in promoting the phase separation reaction. The reaction auxiliary solvent is preferably at least one compound selected from the group consisting of an alcohol compound, a polyol-based ether, a cyclic ether compound, a polyol-based ester, a ketone compound, and a fluorene compound. Examples of the alcohol compound include monohydric alcohols such as methanol, ethanol, and propanol; butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, and triethylene glycol. Diols such as glycols, tripropylene glycol, and polyethylene glycol; triols such as glycerol. Examples of the polyol-based ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, and ethyl ether. Glycol ethyl methyl ether, glycol glycol ether and the like. Examples of the cyclic ether compound include 1,3-dioxane and 1,4-dioxane, and examples of the polyol-based ester include glycol ester compounds such as ethylene glycol acetate. Examples of the ketone compound include acetone, methyl ethyl ketone (hereinafter, also referred to as "MEK"), methyl isobutyl ketone, and the like, and examples of the sulfenyl compound include dimethylsulfinium, Ethylene sulfene and the like. Among these compounds, ethylene glycol monomethyl ether, polyethylene glycol, and 1,4-dioxane are preferred. The reaction auxiliary solvent is not limited to the examples described above, as long as it has the above-mentioned characteristics and exhibits a liquid state during the reaction, it may be a solid, and may be used alone or in combination of two or more. The amount of the reaction auxiliary solvent to be blended is not particularly limited, and it is, for example, 5 parts by mass or more, and preferably 10 to 200 parts by mass based on 100 parts by mass of the phenol compound.

In the heterogeneous reaction step, by using a surfactant, the phase separation reaction can be promoted, the reaction time can be shortened, and the yield can be improved. Examples of the surfactant include soap, α-olefin sulfonate, alkylbenzene sulfonic acid and its salts, alkyl sulfate salts, alkyl ether sulfate salts, phenyl ether ester salts, and polyoxyethylene Anionic surfactants such as alkyl ether sulfate, ether sulfonate, ether carboxylate; polyoxyethylene alkylphenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene styrenated phenol ether, Polyoxyethylene alkylamino ethers, polyethylene glycol aliphatic esters, aliphatic monoglycerides, sorbitan aliphatic esters, pentaerythritol aliphatic esters, polyoxyethylene polypropylene glycol, aliphatic alkanolamines and other non- Ionic surfactants; cationic surfactants such as monoalkylammonium chloride, dialkylammonium chloride, and amine salt compounds. The blending amount of the surfactant is not particularly limited, and is, for example, 0.5 parts by mass or more, and preferably 1 to 10 parts by mass based on 100 parts by mass of the phenol compound.

The amount of water in the reaction system affects the phase separation effect and production efficiency, but it is usually 40% by mass or less on a mass basis. By setting the amount of water to 40% by mass or less, production efficiency can be favorably maintained.

The reaction temperature of the phenol compound and the aldehyde compound varies depending on the type of the phenol compound, the reaction conditions, and the like, and is not particularly limited, but is usually 40 ° C or higher, preferably 80 ° C to a reflux temperature, and more preferably a reflux temperature. When the reaction temperature is 40 ° C or higher, a sufficient reaction rate can be obtained. The reaction time varies depending on the reaction temperature, the amount of phosphoric acid to be formulated, the water content in the reaction system, and the like, and is usually about 1 to 10 hours.

The reaction environment is usually normal pressure, but the reaction may be carried out under pressure or reduced pressure from the viewpoint of maintaining a heterogeneous reaction that is a feature of the present invention. For example, a reaction speed can be increased under a pressure of 0.03 MPa to 1.50 MPa, and a low-boiling-point solvent such as methanol can be used as a reaction auxiliary solvent.

According to the (a) method for producing a novolak phenol resin, a novolak phenol resin having a dispersion ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 1.05 to 1.8 can be produced. Although it varies depending on the type of phenol compound, depending on the range of the molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P), for example, (a) a novolak phenol resin can be obtained as follows . If the molar ratio (F / P) is in the range of 0.33 or more and less than 0.80, the measurement method using the gel permeation chromatography (GPC) area method can be manufactured in high yield as follows: The content of the monomer component of the phenol compound is, for example, 3% by mass or less, preferably 1% by mass or less, and the content of the dimer component of the phenol compound is, for example, 5% to 95% by mass. It is preferably 10% by mass to 95% by mass, and the dispersion ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by GPC measurement is 1.05 to 1.8, and preferably 1.1 to 1.7.

(A) Novolac-type phenol resins may be commercially available. For example, "PAPS-PN2" (produced by Asahi Organic Materials Co., Ltd., trade name), "PAPS-PN3" (Asahi Organic Materials Industry Co., Ltd.) Manufacturing, trade name), etc.

The resin composition for a film may be used together with an epoxy resin hardener (hereinafter, also simply referred to as an "epoxy resin hardener") other than the novolac-type phenol resin within a range that does not inhibit the effects of the present invention. Examples of the epoxy resin curing agent include (a) various phenol resin compounds, acid anhydride compounds, amine compounds, and hydrazine compounds other than novolac-type phenol resins. Examples of the phenol resin compounds include (a) novolac phenol resins and resol phenol resins other than novolac phenol resins, and acid anhydride compounds include phthalic anhydride and benzophenone Tetracarboxylic dianhydride, methyl himic anhydride, etc. Examples of the amine compound include dicyandiamine, diaminodiphenylmethane, and guanylurea.

Among these epoxy resin hardeners, (a) a novolak-type phenol resin other than the novolak-type phenol resin is preferred from the viewpoint of improving reliability. From the viewpoint of improving the peel strength of the metal foil and the peel strength of the electroless plating after chemical roughening, a triazine ring-containing novolac-type phenol resin and dicyandiamine are preferred. (A) Novolac-type phenolic resins other than novolac-type phenolic resins may be commercially available. Examples include phenolic novolac resins such as "TD2090" (manufactured by DIC Corporation, trade name), " "KA-1165" (manufactured by DIC Corporation, trade name) and other cresol novolac resins. Examples of commercially available products of novolac-type phenol resins containing a triazine ring include: "Phenolite LA-1356" (manufactured by DIC Corporation, trade name), and "Finolite" (Phenolite) LA7050 series "(manufactured by DIC Corporation, trade name), and other commercially available products of triazine-containing cresol novolac resins include" Phenolite LA-3018 " (Trade name, manufactured by DIC Corporation), etc.

<(A) Epoxy resin> (A) The epoxy resin is an epoxy resin represented by the following general formula (I).

[Chemical 2]

(Where p is an integer from 1 to 5)

(A) A commercially available epoxy resin can also be used. Commercially available (A) epoxy resins include, for example, "NC-3000" (epoxy resin with p in Formula (1) of 1.7), and "NC-3000-H" (p in Formula (1) Epoxy resin of 2.8) (both manufactured by Nippon Kayaku Co., Ltd., trade name), etc. The resin composition for a film may include a polymer type epoxy resin such as an epoxy resin other than an epoxy resin and a phenoxy resin, as long as the effect of the present invention is not hindered.

<Hardening Accelerator> From the viewpoint of accelerating the reaction between (a) novolac-type phenol resin and (A) epoxy resin, the resin composition for an adhesive film may further include a hardening accelerator. Examples of the hardening accelerator include imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, trimellitic acid 1-cyanoethyl-2-phenylimidazolium, and triphenylphosphine. Organophosphorus compounds; Onium salts such as phosphonium borate; amines such as 1,8-diazabicycloundecene; 3- (3,4-dichlorophenyl) -1,1-dimethylurea. These compounds can be used alone or in combination of two or more.

<(C) Inorganic filler> Next, the resin composition for films contains (c) an inorganic filler whose average particle diameter is 0.1 micrometer or more. (C) Examples of the inorganic filler include silicon dioxide, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, Boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. These compounds can be used alone or in combination of two or more. Among these compounds, silicon dioxide is preferred from the viewpoint of reducing the thermal expansion coefficient of the interlayer insulating layer formed by curing the film. (C) The shape of the inorganic filler is not particularly limited, and is preferably spherical from the viewpoint of being easily buried in the through holes formed in the inner-layer circuit and the irregularities of the circuit pattern.

(C) The average particle diameter of the inorganic filler is 0.1 μm or more, and from the viewpoint of obtaining excellent embedding properties, it is preferably 0.2 μm or more, and more preferably 0.3 μm or more. From the viewpoint of embedding property, the content of the inorganic filler having an average particle diameter of less than 0.1 μm is preferably 3 vol% or less, more preferably 1 vol% or less, and more preferably no average particle diameter, based on the solid content. Inorganic filler less than 0.1 μm. The (c) inorganic filler may be used alone or as a mixture of different average particle diameters.

(C) A commercially available thing can also be used for an inorganic filler. Examples of commercially available (c) inorganic fillers include spherical silica "SO-C1" (average particle size: 0.25 μm), "SO-C2" (average particle size: 0.5 μm), and "SO- "C3" (average particle size: 0.9 μm), "SO-C5" (average particle size: 1.6 μm), "SO-C6" (average particle size: 2.2 μm) (all of which are limited by Admatechs) Company)).

(C) The inorganic filler may be a surface treated. For example, when silicon dioxide is used as the (c) inorganic filler, a silane coupling agent treatment may be performed as a surface treatment. Examples of the silane coupling agent include amine silane coupling agents, vinyl silane coupling agents, and epoxy silane coupling agents. Among these compounds, silicon dioxide which has been surface-treated with an aminosilane coupling agent is preferred.

The amount of the (c) inorganic filler in the resin composition for a film is defined as follows. First, the resin composition forming a layer on the support film was dried at 200 ° C. for 30 minutes, the solvent contained in the resin composition was removed, and the weight (solid content) after removing the solvent was measured. The amount of the (c) inorganic filler contained in the solid content is defined as the amount of the (c) inorganic filler in the resin solid content. In addition, as a measurement method of the (c) inorganic filler, if the amount of the solid content of the (c) inorganic filler prepared in advance is calculated in advance, the ratio of the solid content can be easily determined. A calculation example in the case where (c) an inorganic filler (hereinafter, also referred to as "(c) inorganic filler dispersion liquid") dispersed in a solvent is used is shown below. (C) The solid content of the (c) inorganic filler in the inorganic filler dispersion liquid was dried at 200 ° C for 30 minutes, and the calculated result was 70% by mass. The resin composition was prepared using 40 g of the (c) inorganic filler dispersion, and the total amount of the obtained resin composition was 100 g. 100 g of the resin composition was dried at 200 ° C for 30 minutes, and the weight of the dried solid content was measured. As a result, it was 60 g. The amount of the (c) inorganic filler contained in the solid content is 40 g × 70 mass% = 28 g, so the amount of the (c) inorganic filler in the resin solid content is determined to be 28/60 = 47 mass% ( 46.6% by mass).

From the viewpoint of reducing the thermal expansion coefficient of the interlayer insulating layer after thermal curing, the larger the amount of the (c) inorganic filler in the resin composition for the film, the better, but the wiring of the formed inner-layer circuit board is buried. From the viewpoint of the unevenness of the pattern and the penetration hole, there is an appropriate amount of the inorganic filler. From the viewpoint, the content of the (c) inorganic filler is 20% to 95% by mass, preferably 30% to 90% by mass, and more preferably 50% to 90% by mass in the solid content of the resin. . When the content of the (c) inorganic filler is 20% by mass or more, the thermal expansion coefficient can be reduced, and when it is 95% by mass or less, the embedding property can be kept good.

<Flame Retardant> The resin composition for a film may further contain a flame retardant. The flame retardant is not particularly limited, and examples thereof include inorganic flame retardants and resin flame retardants. Examples of the inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, and the like exemplified as the (c) inorganic filler. The resin flame retardant may be a halogen-based resin or a non-halogen-based resin. In consideration of environmental load, it is preferable to use a non-halogen-based resin. The resin flame retardant may be formulated as a filler, or may have a functional group that reacts with a thermosetting resin. As the resin flame retardant, a commercially available product can be used. Examples of commercially available resin flame retardants formulated as fillers include "PX-200" (a product of Daiba Chemical Industry Co., Ltd.) as an aromatic phosphate ester flame retardant, and polyphosphoric acid. Salt compound "Exolit OP 930" (made by Clariant Japan Co., Ltd., trade name), etc. Examples of commercially available resin flame retardants having a functional group that reacts with a thermosetting resin include epoxy-based phosphorus-containing flame retardants and phenol-based phosphorus-containing flame retardants. Examples of the epoxy-based phosphorus-containing flame retardant include "FX-305" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name). Examples of the phenol-based phosphorus-containing flame retardant include: "HCA-HQ" ( Made by Sanguang Co., Ltd., trade name), "XZ92741" (made by Dow Chemical, trade name), etc. These commercially available products can be used alone or as a mixture of two or more.

<Solvent> From the viewpoint of efficiently forming a layer, the resin composition for an adhesive film preferably contains a solvent. Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, Acetate compounds such as carbitol acetate; carbitol compounds such as cellosolve, methyl carbitol, butyl carbitol; aromatic hydrocarbon compounds such as toluene and xylene; dimethylformamide, Dimethylacetamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and the like. These compounds can be used alone or in combination of two or more.

<Residual solvent amount> The residual solvent amount in the adhesive film of the present invention varies depending on the material to be processed, and is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and even more preferably 2% by mass. % To 10% by mass. When the amount of the residual solvent is 1% by mass or more, the operability of the adhesive film is improved, and, for example, the occurrence of powder fall and the occurrence of cracks when the film is cut by a cutter can be suppressed. On the other hand, when it is 20% by mass or less, blocking is suppressed, and winding and unwinding of the film becomes easy. In addition, in order to expand, a protective film is often provided on the varnish-coated surface of the adhesive film after drying. If the amount of the residual solvent is 20% by mass or less, peeling between the protective film and the adhesive film of the present invention becomes easy. In addition, the residual solvent is removed by drying and thermal curing in the step of manufacturing a multilayer printed wiring board. Therefore, the less the environmental load, the better. In order to reduce the change in film thickness before and after drying and thermal curing, The less, the better. Moreover, when manufacturing the adhesive film of this invention, it is preferable to determine drying conditions so that it may become a target residual solvent amount. The drying conditions vary depending on the type of solvent, the amount of the solvent, and the like contained in the resin composition. Therefore, it is preferable to use various coating devices and determine the conditions in advance.

Here, the amount of the residual solvent in the present invention is the ratio (% by mass) of the solvent contained in the resin composition layer of the support film, and can be defined as follows. First, the weight (W _a ) of the support film is measured, and the weight (W _b ) after the resin composition layer is formed thereon is measured. Then, the support film and the resin composition layer formed thereon were allowed to stand in a dryer at 200 ° C. for 10 minutes, and the weight after drying (W _c ) was measured. The obtained weight (W _a ) to weight (W _c ) can be calculated by the following formula. Proportion of solvent (% by mass) = (1-((W _c )-(W _a )) / ((W _b )-(W _a ))) × 100

<Other components> The adhesive film of this invention may contain other components in the range which does not inhibit the effect of this invention. Other ingredients include, for example, thickeners such as Orben and organic benton; UV absorbers such as thiazole and triazole; adhesion-imparting agents such as silane coupling agents; phthalocyanine blue and phthalocyanine Colorants such as cyanine green, iodine green, disazo yellow, and carbon black; optional resin components other than the above; and the like.

[Supporting Film] The so-called supporting film in the present invention is a supporter at the time of manufacturing the adhesive film of the present invention, and usually is eventually peeled off or removed when manufacturing a multilayer printed wiring board.

The support film is not particularly limited, and examples thereof include an organic resin film, a metal foil, and a release paper. Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; polyethylene terephthalate (hereinafter, also referred to as "PET"), and polymers such as polyethylene naphthalate Ester; polycarbonate, polyimide, etc. Among these compounds, PET is preferred from the viewpoints of price and operability. Examples of the metal foil include copper foil and aluminum foil. When using copper foil for a support body, a copper foil may be used as a conductor layer directly, and a circuit may be formed. In this case, rolled copper, electrolytic copper foil, or the like can be used for the copper foil. The thickness of the copper foil is not particularly limited, and for example, a thickness of 2 to 36 μm can be used. When a thin copper foil is used, a copper foil with a carrier may be used from the viewpoint of improving workability. These support films and a protective film described later may be subjected to surface treatments such as mold release treatment, plasma treatment, and corona treatment. Examples of the release treatment include a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, and a fluororesin-based release agent. The thickness of the support film is not particularly limited. From the viewpoint of operability, it is preferably 10 μm to 120 μm, more preferably 15 μm to 80 μm, and even more preferably 15 μm to 70 μm. The support film does not need to be a single component as described above, and may be formed of a plurality of layers (two or more layers) of other materials.

In the case where the support film has a two-layer structure, for example, the support film described above can be used as the support film of the first layer, and has an epoxy resin, a hardener for epoxy resin, The second layer is a layer formed by a filler or the like. The materials used in the second layer can also be those listed in Materials used in the adhesive film of the present invention. The layer formed on the first layer of the support film (the second layer or less may be a multilayer of two or more layers) is a layer made to impart functions, and may be used for the purpose of improving adhesion with copper plating, for example. use. The method for forming the second layer is not particularly limited, and examples thereof include a method in which a varnish obtained by dissolving and dispersing each material in a solvent is applied to a support film of the first layer and dried.

In the case where the support film is formed of multiple layers, the thickness of the first support film is preferably 10 μm to 100 μm, more preferably 10 μm to 60 μm, and even more preferably 13 μm to 50 μm. The thickness of the layer formed on the support film of the first layer (the second layer may be less than the second layer, or may be two or more layers), and the thickness is preferably 1 μm to 20 μm. If it is 1 μm or more, a desired function can be exhibited, and if it is 20 μm or less, it is excellent in economy as a support film.

In the case where the support film is formed of multiple layers, when the support film is peeled off, it can also be separated into layers remaining on the multilayer printed wiring board side with the adhesive film of the present invention (there can be two or more layers), And the layers that can be stripped or removed (may be two or more).

[Protective film] The adhesive film of the present invention may have a protective film. The protective film is provided on the surface of the adhesive film on the side opposite to the surface on which the support is provided, and is used for the purpose of preventing adhesion of foreign matter and the like and scratching the adhesive film. The protective film is peeled before the adhesive film of the present invention is laminated on a circuit board or the like by lamination, hot pressing, or the like. The protective film is not particularly limited, and the same material as the support film can be used. The thickness of the protective film is not particularly limited, and for example, a thickness of 1 to 40 μm can be used.

[Manufacturing Method of Adhesive Film] The adhesive film of the present invention can be produced by applying a resin composition for an adhesive film to a support film and drying it. The obtained adhesive film can be wound into a roll shape for storage and storage. More specifically, it can be manufactured, for example, by dissolving each resin component in the organic solvent, mixing (c) an inorganic filler, etc. to prepare a resin composition for a film, and applying the varnish. A resin composition layer is formed on the support film by drying the organic solvent by heating, hot air blowing, or the like. In the adhesive film of the present invention, the resin composition layer formed on the support film may be in an uncured state obtained by drying, or may be in a semi-cured state (in a B-stage state).

The method for applying the varnish on the support film is not particularly limited, and for example, a comma coater, a bar coater, a kiss coater, and a roll can be used. A method of applying by a known coating device such as a roll coater, a gravure coater, or a die coater. The coating device may be appropriately selected depending on the target film thickness.

[2] Second invention Next, a resin film for an interlayer insulating layer, a multilayer resin film, and a multilayer printed wiring board according to the second invention will be described.

[Resin film for interlayer insulation layer] The resin film for interlayer insulation layer of the second invention uses a resin containing (A) an epoxy resin, (B) a cyanate resin, (C) an inorganic filler, and (D) a monofunctional phenol compound. A thermosetting resin composition (hereinafter, also referred to as a "resin composition for an interlayer insulating layer") formed of a resin film for an interlayer insulating layer, and 100 parts by mass of the solid content of the thermosetting resin composition (C) The content of the inorganic filler is 50 to 85 parts by mass. In the present specification, the "solid content" is a non-volatile component other than a volatile substance such as a solvent, and means a component that does not evaporate and remains when the resin composition is dried, and also includes a liquid state and a sugar-thin state at room temperature. And waxy ones. Here, in this specification, the room temperature means 25 ° C. The resin film for an interlayer insulating layer is also commonly referred to as an interlayer insulating film.

<Resin composition for interlayer insulation layer> The resin composition for interlayer insulation layers used in the formation of the resin film for interlayer insulation layers of the second invention contains (A) an epoxy resin, (B) a cyanate resin, and (C) ) An inorganic filler and (D) a monofunctional phenol compound. Hereinafter, each component is demonstrated.

[(A) Epoxy Resin] (A) The epoxy resin is not particularly limited. For example, an epoxy resin having two or more epoxy groups in one molecule can be preferably cited. Examples of such (A) epoxy resin include a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin. Among these epoxy resins, a glycidyl ether type epoxy resin is preferable. (A) Epoxy resins are also classified according to different main skeletons. Among the various types of epoxy resins, they are further classified into bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type ring. Epoxy resin and other bisphenol epoxy resin; phenol novolac epoxy resin, alkylphenol novolac epoxy resin, cresol novolac epoxy resin, naphthol alkylphenol copolymer novolac epoxy resin, Novolac epoxy resins such as bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, aralkyl novolac epoxy resin; styrenic epoxy resin; triazine skeleton-containing epoxy resin Epoxy resin; Epoxy resin containing fluorene skeleton; Naphthalene epoxy resin; Triphenylmethane epoxy resin; Biphenyl epoxy resin; Xylene epoxy resin; Dicyclopentadiene epoxy resin And other alicyclic epoxy resin. Examples of the aralkyl novolac epoxy resin include an aralkyl cresol copolymerized novolac epoxy resin having a naphthol skeleton, and an aralkyl novolac epoxy resin having a biphenyl skeleton. (A) The epoxy resin may be used alone or in combination of two or more. Among these, from the viewpoints of the storage stability and operability of the resin film for an interlayer insulating layer, and the electrical characteristics and heat resistance of the interlayer insulating layer obtained, a novolak-type epoxy resin is preferred, and more preferably Cresol novolac epoxy resin, bisphenol A novolac epoxy resin. From the same viewpoint, it is preferable to use a cresol novolac epoxy resin and a bisphenol A novolac epoxy resin in combination. When a cresol novolak-type epoxy resin and a bisphenol A novolac-type epoxy resin are used in combination, the storage stability and operability of the resin film for an interlayer insulating layer, and the electrical characteristics and electrical properties of the obtained interlayer insulating layer and From the viewpoint of heat resistance, the mass ratio (cresol novolac epoxy resin / bisphenol A novolac epoxy resin) is preferably 40/60 to 90/10, and more preferably 50/50 to 80 / 20, particularly preferably 60/40 to 70/30.

From the viewpoint of improving the handleability of the resin film for an interlayer insulating layer, (A) the epoxy resin may contain an epoxy resin that is liquid at room temperature. The liquid epoxy resin is not particularly limited, and examples thereof include bifunctional liquid epoxy resins such as a bisphenol A type liquid epoxy resin. When (A) the epoxy resin contains a liquid epoxy resin, the content of the liquid epoxy resin is higher than that of the (A) epoxy resin from the viewpoint of improving the operability of the resin film for an interlayer insulating layer. It is preferably 2% to 30% by mass, more preferably 4% to 20% by mass, and even more preferably 6% to 15% by mass.

From the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the obtained interlayer insulating layer, the epoxy equivalent of the (A) epoxy resin is preferably 120 g / eq. ~ 500 g / eq, more preferably 150 g / eq to 350 g / eq, and even more preferably 180 g / eq to 250 g / eq. Here, the epoxy equivalent is the resin mass (g / eq) of each epoxy group, and it can be measured according to the method prescribed in Japanese Industrial Standards (JIS) K 7236 (2001). Specifically, using an automatic titration device "GT-200" manufactured by Mitsubishi Chemical Co., Ltd., 2 g of epoxy resin was weighed in a 200 ml beaker, and 90 ml of methyl ethyl was added dropwise. The ketone was dissolved in an ultrasonic scrubber, 10 ml of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and the solution was determined by titration with a 0.1 mol / L perchloric acid / acetic acid solution.

From the viewpoint of the storage stability and operability of the resin film for an interlayer insulating layer, and the electrical characteristics and heat resistance of the interlayer insulating layer obtained, the interlayer is relative to 100 parts by mass of the solid content of the resin composition for the interlayer insulating layer. The content of the (A) epoxy resin in the resin composition for an insulating layer is preferably 5 to 50 parts by mass, more preferably 10 to 35 parts by mass, and even more preferably 15 to 25 parts by mass.

[(B) Cyanate Resin] (B) The cyanate resin is not particularly limited. For example, a cyanate resin having two or more cyano groups in one molecule can be preferably cited. (B) Cyanate resins include 2,2-bis (4-cyanophenyl) propane [bisphenol A cyanate resin], bis (4-cyanophenyl) ethane [bis Phenol E-type cyanate resin], bis (3,5-dimethyl-4-cyanophenyl) methane [tetramethylbisphenol F-type cyanate resin], 2,2-bis (4- Cyanophenyl) -1,1,1,3,3,3-hexafluoropropane [hexafluorobisphenol A type cyanate resin] and other bisphenol type cyanate resins; phenol addition dicyclopentadiene Dicyclopentadiene-based cyanate resins such as cyanate ester compounds of olefin polymers; novolac-based cyanate resins such as phenol novolac-based cyanate ester compounds, cresol novolac-based cyanate ester compounds; α, α'-bis (4-cyanophenyl) -m-isopropylbenzene; prepolymers of these cyanate resins (hereinafter, also referred to as "cyanate prepolymers") and the like. (B) A cyanate resin may be used individually by 1 type, and may use 2 or more types together. Among these, bisphenol-type cyanate resin and novolac are preferable from the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the obtained interlayer insulating layer. Type cyanate resin, and these prepolymers. The bisphenol-type cyanate resin is preferably a dicyanate resin represented by the following general formula (1).

[Chemical 3] (In the formula, R ^B1 represents an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a sulfur atom, which can be substituted with a halogen atom, the following general formula (1-1), or the following formula Divalent group represented by (1-2). R ^B2 and R ^B3 each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

[Chemical 4] ( ^Wherein R ^B4 independently represents an alkylene group having 1 to 5 carbon atoms or an alkylene group having 2 to 5 carbon atoms)

[Chemical 5]

Examples of the alkylene group having 1 to 5 carbon atoms represented by R ^{B1 in} the general formula (1) include methylene, ethylene, 1,2-dimethylene, 1,3-trimethylene, and 1 , 4-tetramethylene, 1,5-pentamethylene and the like. Examples of the alkylene group having 2 to 5 carbon atoms represented by R ^{B1 in} the general formula (1) include ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, and ethylene Isoamyl etc. Examples of the halogen atom that replaces the alkylene group having 1 to 5 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the general formula (1-1), as in the case of R ^B1 in the general formula (1), an alkylene group having 1 to 5 carbon atoms and an alkylene group having 2 to 5 carbon atoms represented by R ^B4 will be described. . Among the groups represented by R ^B1 , a methylene group and a propylene group are preferred, and a propylene group is more preferred. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^B2 and R ^{B3 in} the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary Butyl and so on. R ^B2 and R ^{B3 are} preferably a hydrogen atom.

The so-called cyanate prepolymer refers to a polymer in which cyanate resins form a triazine ring through cyclization reaction, and mainly includes a trimer, a pentamer, and a heptamer of a cyanate ester compound. , Nine polymer, eleven polymer, etc. In this cyanate ester prepolymer, from the viewpoint of obtaining good solubility in an organic solvent, the conversion rate of the cyanate group is preferably from 20% by mass to 70% by mass, and more preferably from 30% by mass to 65% by mass. . From the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the interlayer insulating layer obtained, the cyanate ester prepolymer preferably has two cyanic acid in one molecule. A prepolymer of a dicyanate compound based on a base is more preferably a prepolymer of a dicyanate resin represented by the general formula (1), and at least a part of a bisphenol A-type cyanate resin is particularly preferred. The prepolymer represented by the following formula (2) that is triazinated to become a trimer.

[Chemical 6]

From the viewpoint of the solubility and workability of the organic solvent, the weight average molecular weight (Mw) of the cyanate ester prepolymer is preferably 500 to 4,500, more preferably 600 to 4,000, and even more preferably 1,000 to 4,000. It is preferably 1,500 to 4,000. When the weight average molecular weight of the cyanate prepolymer is 500 or more, the crystallization of the cyanate prepolymer is suppressed, and the solubility in an organic solvent tends to be good. When it is 4,500 or less, the viscosity The increase is suppressed and there is a tendency that the workability is excellent. The weight average molecular weight and the number average molecular weight mentioned later in this invention are the values measured by the gel permeation chromatography (GPC) method (polystyrene conversion), and can be measured by the method as described in an Example.

The cyanate ester prepolymer may be a polymer obtained by prepolymerizing a cyanate resin in the presence of a (D) monofunctional phenol compound described later. Thereby, the unreacted cyano group in the obtained hardened | cured material can be reduced, and there exists a tendency for it to be excellent in moisture resistance and electrical characteristics. By reacting a cyanate resin with a (D) monofunctional phenol compound, a compound having a group represented by -OC (= NH) -O- (i.e., iminocarbonate) is formed, and the The amino carbonates react with each other, or the imine carbonate reacts with a dicyanate compound, (D) the monofunctional phenol compound is removed, and on the other hand, a cyanate prepolymer having a triazine ring is obtained . In the reaction, for example, a cyanate resin and a (D) monofunctional phenol compound may be mixed and dissolved in the presence of a solvent such as toluene, and the reaction may be performed by adding zinc naphthenate if necessary while maintaining the temperature at 80 ° C to 120 ° C. Accelerator to carry out.

When (D) a monofunctional phenol compound is used in the production of a cyanate prepolymer, the amount of the (D) monofunctional phenol compound is preferably (D) a phenolic hydroxyl group possessed by the monofunctional phenol compound. The equivalent ratio (hydroxyl / cyanate group) of the cyanate group to the cyanate resin used as a raw material of the cyanate ester prepolymer is 0.01 to 0.30, more preferably 0.01 to 0.20, especially The amount is preferably 0.01 to 0.15. When the amount of the (D) monofunctional phenol compound is within the above range, in addition to a tendency to obtain a sufficiently low dielectric loss tangent, particularly in a high frequency band, there is also a tendency to obtain good moisture resistance. .

(B) A cyanate resin can also use a commercial item. (B) Commercial products of cyanate ester resins include "Primaset BADCy" (manufactured by Lonza) and "Arocy" as bisphenol A type cyanate resins. ) B-10 "(manufactured by Huntsman)," Arocy L10 "(manufactured by Huntsman) and" Prima "as bisphenol E-type cyanate resins Primaset LECy "(manufactured by Lonza)," Primaset METHYLCy "(manufactured by Lonza) as a tetramethylbisphenol F-type cyanate resin Primaset PT30, a phenol novolac cyanate resin (manufactured by Lonza), etc. Examples of commercially available prepolymers of cyanate resins include "Primaset BA200", "Primaset (200 Primaset) BA230S "," Primaset BA3000S "(the above is made by Lonza) and so on. Examples of the cyanate resin other than the above include "Arocy XU-371" (manufactured by Huntsman), and "Arocy" as a cyanate resin containing a dicyclopentadiene structure. West (Arocy XP71787.02L "(made by Huntsman)," Primaset DT-4000 "(made by Lonza)," Primaset DT -7000 "(manufactured by Lonza).

From the viewpoint of the storage stability and operability of the resin film for an interlayer insulating layer, and the electrical characteristics and heat resistance of the interlayer insulating layer obtained, the interlayer is relative to 100 parts by mass of the solid content of the resin composition for the interlayer insulating layer. The content of the (B) cyanate resin in the resin composition for an insulating layer is preferably 1 to 30 parts by mass, more preferably 2 to 22 parts by mass, and even more preferably 3 to 10 parts by mass.

From the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the obtained interlayer insulating layer, (A) the epoxy resin in the resin composition for an interlayer insulating layer and ( B) The mass ratio [(A) / (B)] of the cyanate resin is preferably 1 to 10, more preferably 2 to 7, and even more preferably 2.5 to 4. When the mass ratio [(A) / (B)] is 1 or more, there is a tendency that the content of the (B) cyanate resin does not become excessive and a rise in the curing temperature can be suppressed, and when it is 10 or less, There is a tendency that the amount of unreacted epoxy groups in the interlayer insulating layer obtained can be reduced.

[(C) Inorganic filling materials] (C) Inorganic filling materials include: silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide , Boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these compounds, silicon dioxide is preferred from the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the interlayer insulating layer to be obtained. (C) The inorganic filler may be used alone or in combination of two or more.

From the viewpoint of obtaining a good embedding property of the circuit board and the viewpoint of insulation reliability, the volume average particle diameter of the (C) inorganic filler is preferably 0.01 μm to 5 μm, more preferably 0.1 μm to 2 μm, It is particularly preferably 0.2 μm to 1 μm. In addition, when the volume average particle diameter is 100% of the total volume of the particles and the cumulative degree distribution curve of the particle diameter is obtained, the particle diameter of the point corresponding to 50% of the volume can be obtained by using laser diffraction scattering method. Particle size distribution measuring device. From the viewpoint of pattern embedding, the shape of the (C) inorganic filler is preferably spherical.

(C) A commercially available thing can also be used for an inorganic filler. Commercially available (C) inorganic fillers include spherical silica "SO-C1" (volume average particle size: 0.25 μm), "SO-C2" (volume average particle size: 0.5 μm), and "SO -C3 "(volume average particle size: 0.9 μm)," SO-C5 "(volume average particle size: 1.6 μm)," SO-C6 "(volume average particle size: 2.2 μm) (above are Yaduma Technology ( Admatechs).

From the viewpoint of improving the moisture resistance, the (C) inorganic filler may be a surface treated with a silane coupling agent. Examples of the silane coupling agent include amine silane coupling agents, epoxy silane coupling agents, phenyl silane coupling agents, alkyl silane coupling agents, alkenyl silane coupling agents, mercapto silane coupling agents, and isocyanate silanes. Couplings, etc. Among these silane coupling agents, from the viewpoint of storage stability of the resin composition for an interlayer insulating layer, an amine silane coupling agent is preferred. The surface treatment method using the silane coupling agent may be a dry or wet surface treatment method of the inorganic filler before preparation, or may be a method in which the inorganic filler having no surface treatment and other ingredients are formulated into a composition, and then This composition is a so-called integral blend processing method in which a silane coupling agent is added.

From the viewpoint of low thermal expansion, high-frequency characteristics, and embedding properties in the wiring pattern, (C) in the resin composition for the interlayer insulating layer is 100 parts by mass of the solid content of the resin composition for the interlayer insulating layer. The content of the inorganic filler is 50 to 85 parts by mass, preferably 55 to 80 parts by mass, and more preferably 60 to 75 parts by mass. When the content of the (C) inorganic filler is 50 parts by mass or more, there is a tendency to obtain good low thermal expansion properties and high-frequency characteristics. When the content is 85 parts by mass or less, good embedding properties in the wiring pattern are obtained. Propensity.

[(D) Monofunctional phenol compound] The resin composition for an interlayer insulating layer contains (D) a monofunctional phenol compound. The resin film for an interlayer insulating layer of the present invention is formed by using a resin composition for an interlayer insulating layer containing a (D) monofunctional phenol compound, and is excellent in electrical characteristics, heat resistance, storage stability, and handling properties.

(D) Examples of the monofunctional phenol compound include a compound represented by the following general formula (3-1), a compound represented by the following general formula (3-2), and a compound represented by the following general formula (3-3) Compounds etc.

[Chemical 7] (In the formula, R ^D1 each independently represents an alkyl group having 1 to 10 carbon atoms, and m1 represents an integer of 0 to 5)

[Chemical 8] (In the formula, R ^D2 and R ^D3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Ar ^D1 each independently represents an aryl group having 6 to 20 carbon atoms, and m 2 represents an integer of 1 to 5)

[Chemical 9] (In the formula, R ^D4 each independently represents an alkylene group having 1 to 5 carbon atoms, Ar ^D2 each independently represents an aryl group having 6 to 20 carbon atoms, and m3 represents an integer of 1 to 5)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{D1 in} the general formula (3-1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. Base, n-pentyl, octyl, nonyl, etc. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred. In the general formula (3-1), m1 represents an integer of 0 to 5, preferably an integer of 1 to 4, and more preferably an integer of 2 to 4.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^D2 and R ^{D3 in} the general formula (3-2) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Third butyl, n-pentyl and the like. Among these, a methyl group is preferable. Examples of the aryl group having 6 to 20 carbon atoms represented by Ar ^{D1 in} the general formula (3-2) include phenyl, naphthyl, anthryl, and biphenyl. Among these, phenyl is preferred. In the general formula (3-2), m2 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2, and even more preferably 1.

Examples of the alkylene group having 1 to 5 carbon atoms represented by R ^{D4 in} the general formula (3-3) include methylene, ethylene, 1,2-dimethylene, and 1,3-trimethylene. , 1,4-tetramethylene, 1,5-pentamethylene and the like. Among these, methylene is preferred. Examples of the aryl group having 6 to 20 carbon atoms represented by Ar ^{D1 in} the general formula (3-3) include a phenyl group, a naphthyl group, an anthryl group, and a biphenyl group. Among these, phenyl is preferred. In the general formula (3-3), m3 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2, and even more preferably 1.

Examples of the compound represented by the general formula (3-1) include cresol, 3-ethylphenol, p-third butylphenol, p-third pentylphenol, p-third octylphenol, and p-nonyl. Alkyl-substituted phenol compounds such as phenol, 2,3-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, and 2,3,6-trimethylphenol. Examples of the compound represented by the general formula (3-2) include p- (α-cumyl) phenol and 4-benzylphenol. Examples of the compound represented by the general formula (3-3) include 4- (benzyloxy) phenol, 3- (benzyloxy) phenol, and 2- (benzyloxy) phenol. Among these, 2,3,6-trimethylphenol is preferable from the viewpoints of storage stability and operability of the resin film for an interlayer insulating layer, and electrical characteristics and heat resistance of the interlayer insulating layer to be obtained. , P- (α-cumyl) phenol, 4- (benzyloxy) phenol. (D) A monofunctional phenol compound may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of the storage stability and operability of the resin film for an interlayer insulating layer, and the electrical characteristics and heat resistance of the obtained interlayer insulating layer, it is used for the interlayer insulating layer with respect to 100 parts by mass of the (B) cyanate resin. The content of the (D) monofunctional phenol compound in the resin composition is preferably 0.5 parts by mass to 35 parts by mass, more preferably 1 part by mass to 30 parts by mass, even more preferably 1.5 parts by mass to 25 parts by mass, and particularly preferably 2 parts by mass to 20 parts by mass, preferably 2 parts by mass to 15 parts by mass, and most preferably 2 parts by mass to 12 parts by mass. When (B) the cyanate resin contains a cyanate prepolymer prepared using the (D) monofunctional phenol compound as described above, (D) used as a raw material of the cyanate prepolymer The monofunctional phenol compound is not included in the content of the (D) monofunctional phenol compound.

[(E) Phenoxy Resin] The resin composition for an interlayer insulating layer preferably contains (E) a phenoxy resin. Herein, the "phenoxy resin" is a generic term for a polymer having a main chain having a multi-addition structure of an aromatic diol and an aromatic diglycidyl ether, and in this specification, it means a weight average molecular weight of 10,000 or more. In addition, when the polymer whose main chain is a multi-addition structure of an aromatic diol and an aromatic diglycidyl ether has an epoxy group, a polymer having a weight average molecular weight of 10,000 or more is classified as (E) a phenoxy resin. The ones with a weight average molecular weight of less than 10,000 are classified as (A) epoxy resins.

From the viewpoint of improving the handleability of the resin film for an interlayer insulating layer, the (E) phenoxy resin preferably contains an alicyclic structure. Here, the "alicyclic structure" refers to "except aromatic compounds among organic compounds in which carbon atoms are bonded to a cyclic structure". Among these, one or more types selected from cyclic saturated hydrocarbons (cycloalkanes) and cyclic unsaturated hydrocarbons (i.e., those containing a double bond (cycloolefin) in the ring) are preferred. (E) The phenoxy resin includes a phenoxy resin containing a cyclohexane structure, a phenoxy resin containing a trimethylcyclohexane structure, and a phenoxy resin containing a terpene structure. Among these, from the viewpoint of improving the operability of the resin film for an interlayer insulating layer, a phenoxy resin containing one or more selected from the group consisting of a terpene structure and a trimethylcyclohexane structure is more preferable, and more preferably A phenoxy resin containing a trimethylcyclohexane structure. Examples of phenoxy resins containing a trimethylcyclohexane structure include the bisphenol TMC (bis (4-hydroxyphenyl) -3,3,5-trimethyl) disclosed in Japanese Patent Laid-Open No. 2006-176658. Cyclohexane) Phenoxy resin etc. as raw materials. Examples of the phenoxy resin having a terpene structure include the phenoxy resin disclosed in Japanese Patent Laid-Open No. 2006-176658. As a raw material diphenol compound, terpene diphenol is used instead of bis (4-hydroxybenzene). Group) -3,3,5-trimethylcyclohexane and other phenoxy resins. (E) A phenoxy resin may be used individually by 1 type, and may use 2 or more types together.

(E) The weight average molecular weight of the phenoxy resin is preferably 10,000 to 60,000, more preferably 12,000 to 50,000, particularly preferably 15,000 to 45,000, particularly preferably 17,000 to 40,000, and extremely preferably 20,000 to 37,000. When the weight average molecular weight of the (E) phenoxy resin is equal to or more than the lower limit value, there is a tendency that an excellent peel strength from the conductor layer is obtained. When the weight average molecular weight is not more than the upper limit value, increase in roughness can be prevented. And an increase in thermal expansion.

The manufacturing method of (E) a phenoxy resin can be manufactured by the bisphenol compound containing a trimethylcyclohexane structure, the bisphenol compound containing a terpene structure, and a bifunctional epoxy resin, for example. As a raw material, according to a well-known manufacturing method of a phenoxy resin, the reaction is performed within the range of the equivalent ratio of an epoxy group and a phenolic hydroxyl group (phenolic hydroxyl group / epoxy group), for example, to 1 / 0.9 to 1 / 1.1.

(E) As a phenoxy resin, a commercial item can be used. The commercially available (E) phenoxy resin preferably contains a bisphenol compound derived from a biphenyl type epoxy resin and a trimethylcyclohexane structure (1,1-bis (4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane), "jER (registered trademark) YX7200B35" (manufactured by Mitsubishi Chemical Co., Ltd., trade name).

When the resin composition for an interlayer insulating layer contains (E) a phenoxy resin, the content thereof is preferably 0.2 to 10 parts by mass relative to 100 parts by mass of the solid content of the resin composition for the interlayer insulating layer. It is preferably 1 to 7 parts by mass, and particularly preferably 2 to 4 parts by mass. When the content of the (E) phenoxy resin is 0.2 parts by mass or more, there is a tendency that the flexibility and handleability are excellent and the peel strength of the conductor layer is excellent. When the content is 10 parts by mass or less, storage stability and flowability are present. It is excellent and tends to obtain appropriate roughness.

[(F) Active ester hardener] The resin composition for an interlayer insulating layer preferably contains (F) an active ester hardener. By containing the (F) active ester hardener, there is a tendency to reduce the dielectric loss tangent. (F) The active ester hardener is not particularly limited, and examples thereof include compounds having two or more ester groups in one molecule. Specific examples include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxyl compounds.

(F) The active ester hardener is preferably obtained by a condensation reaction of one or more members selected from a carboxylic acid compound and a thiocarboxylic acid compound and one or more members selected from a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and more preferably, it is composed of a carboxylic acid compound and one or more selected from a phenol compound and a naphthol compound. The active ester hardener obtained. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of phenol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylation Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol (phloroglucin ), Trimerol, dicyclopentadienyl diphenol, phenol novolac, etc. Examples of the naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. These compounds can be used alone or in combination of two or more.

(F) As the active ester hardener, the active ester hardener disclosed in Japanese Patent Laid-Open No. 2004-277460 can be used, and a commercially available product can also be used. Examples of commercially available (F) active ester hardeners include those containing a dicyclopentadienyl diphenol structure, an acetic acid compound of a phenol novolac, a benzoic acid compound of a phenol novolac, and the like. Examples of structures containing dicyclopentadienyl diphenol include: "EXB9451", "EXB9460", "EXB9460S-65T", "HPC-8000-65T" (the above are manufactured by DIC Corporation, active groups The equivalent is 223 g / eq). Examples of the acetic acid compound of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent: 149 g / eq). Examples of benzamidine compounds of phenol novolac: "YLH1026" (reactive group equivalent 200 g / eq), "YLH1030" (reactive group equivalent 201 g / eq), "YLH1048" (reactive group equivalent 245 g / eq) (the above are manufactured by Mitsubishi Chemical Co., Ltd.) and the like. Among these, from the viewpoint of the storage stability of the varnish and the thermal expansion coefficient of the cured product, and from the viewpoint of obtaining an interlayer insulating layer excellent in reflow heat resistance, storage stability, and slag removal, it is preferable to include a bicyclic ring. "HPC-8000-65T" with pentadienyl diphenol structure.

When the resin composition for an interlayer insulating layer contains (F) an active ester hardener, from the viewpoint of obtaining excellent electrical characteristics, the active ester group derived from the (F) active ester hardener and the (A) The epoxy resin equivalent ratio (active ester group / epoxy group) is preferably 0.1 to 0.7, more preferably 0.2 to 0.6, and even more preferably 0.3 to 0.5.

[(G) Hardening Accelerator] The resin composition for an interlayer insulating layer may also contain a (G) hardening accelerator from the viewpoint that hardening can be performed at a low temperature for a short time. (G) The hardening accelerator includes a metal-based hardening accelerator, an organic-based hardening accelerator, and the like.

(Metal-based hardening accelerator) As the metal-based hardening accelerator, for example, an organometallic hardening accelerator can be used. The organometallic hardening accelerator has (B) the promotion effect of the self-polymerization reaction of the cyanate resin and (A) the reaction action of the epoxy resin and (B) the cyanate resin. Examples of the organometallic hardening accelerator include transition metals, organometallic salts of Group 12 metals, and organometallic complexes. Examples of the metal include copper, cobalt, manganese, iron, nickel, zinc, and tin. Examples of the organometallic salt include carboxylates, and specific examples thereof include naphthenates such as cobalt naphthenate and zinc naphthenate; 2-ethyl cobalt such as cobalt 2-ethylhexanoate and zinc 2-ethylhexanoate Caproate; zinc octoate, tin octoate; tin stearate, zinc stearate, etc. Examples of the organometallic complex include chelate complexes such as acetoacetone complex, and specific examples thereof include organocobalt complexes such as cobalt (II) acetoacetate and cobalt (III) acetoacetate ; Organic copper complexes such as copper (II) acetamate; organic zinc complexes such as zinc (II) acetamate; organic iron complexes such as iron (III) acetamate; acetamidine pyruvate Organonickel complexes such as nickel (II); organomanganese complexes such as manganese (II) acetamidine. Among these complexes, from the viewpoints of hardenability and solubility, cobalt (II) acetamidine pyruvate, cobalt (III) acetamidine pyruvate, zinc (II) acetamidine pyruvate, and acetamidine are preferred. Iron (III) pyruvate, zinc naphthenate, cobalt naphthenate. These can be used alone or in combination of two or more.

When the resin composition for an interlayer insulating layer contains a metal-based hardening accelerator, from the viewpoint of reactivity and storage stability, the metal-based hardening accelerator is more effective than the solid content mass of the (B) cyanate resin. The content is preferably 10 ppm to 500 ppm by mass, more preferably 50 ppm to 400 ppm, and even more preferably 150 ppm to 300 ppm. The metal-based hardening accelerator can be formulated once or divided into multiple times.

(Organic Hardening Accelerator) The organic hardening accelerator (excluding the organometallic hardening accelerator is not included) can be exemplified by amine compounds such as organic phosphorus compounds, imidazole compounds, secondary amines, and tertiary amines; Ammonium salts, etc. These can be used alone or in combination of two or more. Among these, an organic phosphorus compound, an imidazole compound, and an amine-based compound are preferable, and an organic phosphorus compound is more preferable from the viewpoint of the scum-removability in the via hole. The organic hardening accelerator can be formulated once or divided into multiple times.

Examples of the organic phosphorus compound include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and tricyclohexyl Phosphine, triphenylphosphine / triphenylborane complex, tetraphenylphosphonium tetraphenylborate, addition reaction product of a phosphine compound and a quinone compound having at least one alkyl group bonded to a phosphorus atom, and the like. Among these, an addition reaction product of a triphenylphosphine, a phosphine compound having at least one alkyl group bonded to a phosphorus atom, and a quinone compound is preferred. The addition reaction product of a phosphine compound having at least one alkyl group bonded to a phosphorus atom and a quinone compound is preferably a phosphine having one or more alkyl groups bonded to a phosphorus atom represented by the following general formula (G-1). An addition reaction product of a compound and a quinone compound represented by the following general formula (G-2).

[Chemical 10] (In the general formula (G-1), R ^G1 represents an alkyl group having 1 to 12 carbon atoms, and R ^G2 and R ^G3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; in the general formula (G-2) R ^G4 to R ^G6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^G4 and R ^G5 may be bonded to each other to form a cyclic structure)

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^G1 in the general formula (G-1) include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, and Chain alkyl groups such as tributyl, pentyl, hexyl, octyl, decyl, dodecyl; cyclic alkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, and cyclohexenyl ; Aryl-substituted alkyl groups such as benzyl; alkoxy-substituted alkyl groups such as methoxy-substituted alkyl groups, ethoxy-substituted alkyl groups, butoxy-substituted alkyl groups; Amino-substituted alkyl groups such as aminoamino and diethylamino groups; alkyl groups substituted with hydroxyl groups and the like. Examples of the hydrocarbon group having 1 to 12 carbons represented by R ^G2 and R ^G3 include a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbons, and a substituted or unsubstituted carbon group having 1 to 12 carbons. An alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms, and the like. Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms include the same groups as the alkyl group having 1 to 12 carbon atoms represented by the aforementioned R ^{G 1} . Examples of substituted or unsubstituted alicyclic hydrocarbon groups having 1 to 12 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, and cyclohexenyl. These groups are substituted with alkane Groups such as alkyl, alkoxy, aryl, hydroxyl, amine, and halogen. Examples of substituted or unsubstituted aromatic hydrocarbon groups having 1 to 12 carbon atoms include aryl groups such as phenyl and naphthyl; tolyl, dimethylphenyl, ethylphenyl, butylphenyl, and tert-butyl Alkyl-substituted aryl groups such as phenylphenyl, dimethylnaphthyl; methoxyphenyl, ethoxyphenyl, butoxyphenyl, third butoxyphenyl, methoxynaphthyl, etc. Alkoxy-substituted aryl groups; amine-substituted aryl groups such as dimethylamino and diethylamino groups; halogen-substituted aryl groups such as hydroxyphenyl and dihydroxyphenyl groups; phenoxy and toluene An aryloxy group such as an oxy group; a phenylthio group, a tolylthio group, a diphenylamino group, and these groups are substituted with an amine group, a halogen group, or the like. Among them, a substituted or unsubstituted alkyl group and an aryl group are preferred.

Examples of the phosphine compound represented by the general formula (G-1) include trialkylphosphine such as tricyclohexylphosphine, tributylphosphine, and trioctylphosphine; cyclohexyldiphenylphosphine and dicyclohexylphenylphosphine Alkyldiphenylphosphine, such as butyldiphenylphosphine, dibutylphenylphosphine, octyldiphenylphosphine, dioctylphenylphosphine; dialkylphenylphosphine, etc .; From a viewpoint, tributylphosphine, tris (p-methylphenyl) phosphine, tris (m-methylphenyl) phosphine, and tris (o-methylphenyl) phosphine are particularly preferable.

Examples of the hydrocarbon group having 1 to 18 carbon atoms represented by R ^G4 to R ^G6 in the general formula (G-2) include a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms and 1 to 18 carbon atoms. Substituted or unsubstituted alicyclic hydrocarbon group, substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms, and the like. Examples of substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, third butyl, pentyl, and hexyl , Octyl, decyl, dodecyl and other alkyl groups; vinyl, allyl, propenyl, butenyl and other alkenyl groups; methoxy, ethoxy, propoxy, n-butoxy, Alkoxy groups such as tributoxy; alkylamino groups such as dimethylamino, diethylamino; alkyl groups such as methylthio, ethylthio, butylthio, and dodecylthio Thio; alkyl substituted with amine, alkyl substituted with alkoxy, alkyl substituted with hydroxy, alkyl substituted with aryl, etc. alkyl substituted with amine, A substituted alkoxy group such as a hydroxy-substituted alkoxy group, an aryl group-substituted alkoxy group, and the like. Examples of substituted or unsubstituted alicyclic hydrocarbon groups having 1 to 18 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, and cyclohexenyl. These groups are substituted with alkane Groups such as alkyl, alkoxy, aryl, hydroxyl, amine, and halogen. Examples of substituted or unsubstituted aromatic hydrocarbon groups having 1 to 18 carbon atoms include aryl groups such as phenyl and tolyl; dimethylphenyl, ethylphenyl, butylphenyl, and third butylphenyl And other alkyl-substituted aryl groups; methoxyphenyl, ethoxyphenyl, butoxyphenyl, third butoxyphenyl and other alkoxy-substituted aryl groups; phenoxy, tolueneoxy An aryloxy group such as a phenyl group; a phenylthio group, a tolylthio group, a diphenylamino group, and these groups are substituted with an amine group, a halogen group, or the like. Among them, preferred are: a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group , Substituted or unsubstituted alkylthio, and substituted or unsubstituted arylthio.

In addition, R ^G4 and R ^G5 of the quinone compound represented by the general formula (G-2) may be bonded to form a cyclic structure. Examples of the quinone compound in which R ^G4 and R ^{G5 are} bonded to form a cyclic structure include the following general formula (G-3) to General formula (G to 5) A polycyclic quinone compound represented by any one of the above.

[Chemical 11] (In the general formula (G-3) to the general formula (G-5), R ^G6 is the same as the general formula (G-2))

Among the quinone compounds represented by the general formula (G-2), from the viewpoint of reactivity with a phosphine compound, 1,4-benzoquinone and methyl-1,4-benzoquinone are preferred; From the viewpoint of curability when wet, 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, and methoxy-1 are preferred. 1,4-benzoquinone substituted with alkoxy groups such as 1,4-benzoquinone; 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, methyl formaldehyde Alkyl-substituted 1,4-benzoquinones such as phenyl-1,4-benzoquinone; from the viewpoint of storage stability, 2,5-di-third-butyl-1,4-benzoquinone is preferred , Third butyl-1,4-benzoquinone, phenyl-1,4-benzoquinone.

Examples of the addition reaction product of the phosphine compound represented by the general formula (G-1) and the quinone compound represented by the general formula (G-2) include compounds represented by the following general formula (G-6). .

[Chemical 12] (In the general formula (G-6), R ^G1 to R ^{G6 are the} same as the general formula (G-1) and the general formula (G-2))

Examples of a method for producing an addition reaction product of a phosphine compound and a quinone compound having at least one alkyl group bonded to a phosphorus atom include, for example, adding a phosphine compound and a quinone compound used as raw materials in an organic solvent in which both are dissolved. After the reaction, a separation method is performed. The addition reaction product of a phosphine compound and a quinone compound having at least one alkyl group bonded to a phosphorus atom may be used alone or in combination of two or more.

When the resin composition for an interlayer insulating layer contains an organic hardening accelerator, from the viewpoint of reactivity and storage stability, the content of the organic hardening accelerator is greater than (A) 100 parts by mass of the epoxy resin. It is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.01 to 2 parts by mass.

<Other Components> The resin composition for an interlayer insulating layer may contain components other than the above components within a range that does not inhibit the effects of the present invention. Examples of the other components include resin components (hereinafter, also referred to as “other resin components”), additives, and flame retardants other than the aforementioned components.

(Other resin components) Examples of other resin components include a polymer of a bis-cis-butene-diimide compound and a diamine compound, a bis-cis-butene-di-imide compound, a bis-allyl-diacetimide resin, and benzene. And oxazine compounds.

(Additives) Examples of the additives include thickeners such as oruben and organic soil; adhesion-imparting agents such as imidazole, thiazole, triazole, and silane coupling agents; rubber particles; and colorants.

(Flame retardant) Examples of the flame retardant include inorganic flame retardants and resin flame retardants. Examples of the inorganic flame retardant include aluminum hydroxide and magnesium hydroxide. The resin flame retardant may be a halogen-based resin or a non-halogen-based resin. In consideration of environmental load, a non-halogen-based resin is preferred.

The resin composition for an interlayer insulation layer can be manufactured by mixing (A) component-(D) component, (E) component-(G) component, and other components contained as needed. As the mixing method, a known method can be applied, and for example, a bead mill or the like may be used for mixing.

<Thickness of Resin Film for Interlayer Insulation Layer> The thickness of the resin film for interlayer insulation layer can be determined by, for example, the thickness of a conductor layer formed on a printed wiring board. The thickness of the conductor layer is usually 5 μm to 70 μm. Therefore, the thickness of the resin film for the interlayer insulating layer is preferably 10 μm to 100 μm. From the viewpoint of reducing the thickness of the multilayer printed wiring board, it is more preferably 15 μm. ~ 80 μm, particularly preferably 20 μm to 50 μm.

<Support> The resin film for an interlayer insulating layer of the present invention may be one formed on a support. Examples of the support include organic resin films, metal foils, and release paper. Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate; polycarbonates Ester, polyimide, etc. Among these, PET is preferable from a viewpoint of price and operability. Examples of the metal foil include copper foil and aluminum foil. When using copper foil for a support body, a copper foil may be used as a conductor layer directly, and a circuit may be formed. In this case, rolled copper, electrolytic copper foil, or the like can be used for the copper foil. The thickness of the copper foil can be, for example, 2 μm to 36 μm. When a thin copper foil is used, a copper foil with a carrier may be used from the viewpoint of improving workability.

Surface treatments such as a mold release treatment, a plasma treatment, and a corona treatment may be performed on these supports and a protective film described later. Examples of the release treatment include a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent. From the viewpoint of operability and economy, the thickness of the support is preferably 10 μm to 120 μm, more preferably 15 μm to 80 μm, and even more preferably 25 μm to 50 μm. When manufacturing a multilayer printed wiring board, a support body is usually finally peeled or removed.

<Protective film> A protective film may be arranged on the surface of the resin film for an interlayer insulating layer of the present invention on the side opposite to the support. The protective film is provided on the surface of the resin film for an interlayer insulating layer on the side opposite to the surface on which the support is provided, and is used for the purpose of preventing the adhesion of foreign matter and the like and scratching the resin film for the interlayer insulating layer. The protective film is peeled before a resin film for an interlayer insulating layer is laminated on a circuit board or the like by lamination, hot pressing, or the like. The protective film can be made of the same material as the support. Regarding the thickness of the protective film, for example, one having a thickness of 1 to 40 μm can be used.

<The manufacturing method of the resin film for interlayer insulation layers> The resin film for interlayer insulation layers of this invention can be manufactured, for example, after apply | coating the resin composition for interlayer insulation layers on a support body, and drying. In this case, the resin composition for an interlayer insulating layer is preferably dissolved and / or dispersed in an organic solvent to form a varnish.

(Organic solvents) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (hereinafter also referred to as "MEK"), methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, Cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and other acetate-based solvents; Cellosolve, butyl carbitol, and other carbitol-based solvents; toluene, xylene, and other aromatic solvents Group hydrocarbon solvents; amine solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more. Among these solvents, from the viewpoint of solubility, a ketone-based solvent is preferred, and MEK and methyl isobutyl ketone are more preferred.

As a method for applying the resin composition for an interlayer insulating layer, a known method such as a notch wheel coater, a rod coater, an anastomotic coater, a roll coater, a gravure coater, and a die coater can be applied. Method for applying by applying device. The coating device may be appropriately selected depending on the target film thickness.

The drying conditions after applying the resin composition for an interlayer insulating layer are preferably such that the content of the organic solvent in the obtained interlayer insulating layer resin film becomes 10% by mass or less, and more preferably 5% by mass. Drying was performed in the following manner. Drying conditions also vary according to the amount and type of organic solvent in the varnish. For example, if the varnish contains 20% to 80% by mass of organic solvent, it only needs to be dried at 50 ° C to 150 ° C for 1 minute to 10 minutes. can.

[Multilayer Resin Film] The multilayer resin film of the present invention includes a resin composition layer for an interlayer insulating layer and an adhesive auxiliary layer including the resin film for an interlayer insulating layer of the present invention.

<Resin composition layer for interlayer insulation layer> The resin composition layer for interlayer insulation layer is a layer containing the resin film for interlayer insulation layers of the present invention, and its preferred aspect is as described in the resin film for interlayer insulation layers of the present invention. . The resin composition layer for an interlayer insulation layer is a layer provided between a circuit board and an auxiliary layer when a multilayer printed wiring board is produced using the multilayer resin film of the present invention, and the resin composition layer for the interlayer insulation layer is used. The cured insulating layer plays a role of insulating multilayered circuit patterns from each other in, for example, a multilayer printed wiring board. In addition, when there are through-holes, vias, and the like on the circuit board, the resin composition layer for an interlayer insulating layer also flows through these holes to fill the holes.

The thickness of the resin composition layer for an interlayer insulating layer can be determined according to the thickness of a conductor layer formed on a printed wiring board. The thickness of the conductive layer is usually 5 μm to 70 μm. Therefore, the thickness of the resin composition layer for the interlayer insulating layer is preferably 10 μm to 100 μm. From the viewpoint of reducing the thickness of the multilayer printed wiring board, it is more preferable. 15 μm to 80 μm, particularly preferably 20 μm to 50 μm.

<Next Auxiliary Layer> The next auxiliary layer is a layer that plays a role of insulating the multilayered circuit patterns from each other and smoothing them to increase the peeling strength of the plating in a multilayer printed wiring board that is multilayered by a build-up method. From the viewpoint of obtaining an interlayer insulating layer having high adhesion to the conductor layer, the thickness of the adhesion auxiliary layer is preferably 1 μm to 10 μm, and more preferably 2 μm to 8 μm. The auxiliary layer can be formed using a resin composition for an auxiliary layer.

(Resin composition for auxiliary layer) From the viewpoint of obtaining an interlayer insulating layer having a smooth surface and high adhesion to the conductor layer, the resin composition for the auxiliary layer preferably contains (H) cyanate resin. .

[(H) Cyanate Resin] Examples of the (H) cyanate resin are the same as the (B) cyanate resin contained in the resin composition for an interlayer insulating layer, and preferred embodiments are also the same. When the resin composition for the auxiliary auxiliary layer contains (H) cyanate resin, the resin for the auxiliary auxiliary layer is obtained from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and a high adhesion to the conductor layer. The solid content of the composition is 100 parts by mass, and the content of the (H) cyanate resin is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 20 to 35 parts by mass. .

[(J) Epoxy resin] The resin composition for the auxiliary layer preferably further contains (J) an epoxy resin. (J) The epoxy resin is the same as the (A) epoxy resin which can be contained in the resin composition for an interlayer insulating layer. Among these, an aralkyl novolak-type epoxy resin is preferable, and an aralkyl novolak-type ring which has a biphenyl skeleton is more preferable at the point which is excellent in the reflow heat resistance of the interlayer insulation layer obtained. Oxygen resin. The aralkyl novolak-type epoxy resin having a biphenyl skeleton refers to an aralkyl novolak-type epoxy resin containing an aromatic ring of a biphenyl derivative in a molecule, and examples thereof include the following formula (4) The structural unit is represented by epoxy resin and the like.

[Chemical 13] ( ^Wherein R ^J1 represents a hydrogen atom or a methyl group)

From the viewpoint of obtaining an interlayer insulating layer having a small surface roughness after slag removal and an excellent bonding strength with a conductor layer formed by a plating method, the epoxy resin containing the structural unit represented by the general formula (4) The content of the structural unit represented by the general formula (4) is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass. From the same viewpoint, the epoxy resin containing a structural unit represented by the general formula (4) is preferably an epoxy resin represented by the following general formula (4 ').

[Chemical 14] (Wherein, R ^J1 same as in the general formula (4) R ^J1, s represents an integer of 1 to 20)

In general formula (4 '), from the viewpoint of reducing the surface roughness after slag removal, s is preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.

When the resin composition for an auxiliary layer contains (J) epoxy resin, from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and a high adhesion to a conductor layer, the resin composition for an auxiliary layer is compared with the resin composition for an auxiliary layer. The solid content of the product is 100 parts by mass, and the content of the (J) epoxy resin is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass. In addition, from the viewpoint of obtaining an interlayer insulating layer having high adhesion to the conductor layer, the mass ratio of (J) epoxy resin to (H) cyanate resin in the resin composition for the auxiliary layer [(J) / (H)] is preferably 0.5 to 5, more preferably 1 to 3, and even more preferably 1.2 to 2.5.

[(K) At least one selected from the group consisting of polyamidoamine resin, polyamidoimide resin, and polybenzoxazole resin] Next, the resin composition for the auxiliary layer preferably further contains (K) At least one selected from the group consisting of polyamidoamine resin, polyamidoimide resin, and polybenzoxazole resin. Among these, from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and an excellent bonding strength with a conductor layer formed by a plating method, it is preferable to contain a polyamide resin.

From the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and an excellent bonding strength with a conductive layer formed by a plating method, the polyamide resin used as the (K) component preferably contains a thermosetting resin ( For example, a functional group (such as a phenolic hydroxyl group, an amine group, and the like) that reacts with an epoxy group of an epoxy resin is more preferably one containing a phenolic hydroxyl group. Moreover, from the same viewpoint, it is preferable that the polyamine resin used as a (K) component further contains a polybutadiene skeleton. Such a polyamide resin preferably contains a structural unit represented by the following general formula (5-1), a structural unit represented by the following general formula (5-2), and a structure represented by the following general formula (5-3) The structural unit represented by a phenolic hydroxyl-containing polybutadiene-modified polyamidoamine resin.

[Chemical 15]

[Chemical 16]

[Chemical 17]

In the general formulae (5-1) to (5-3), a, b, c, x, y, and z are average polymerization degrees, a represents an integer of 2 to 10, and b represents an integer of 0 to 3. c represents an integer of 3 to 30, with respect to x = 1, y + z = 2 to 300 ((y + z) / x), and furthermore, z ≧ 20 (z / y) with respect to y = 1. R ^K1 , R ^K2, and R ^K3 are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and R ^K4 is derived from an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or having Divalent group of a carboxyl oligomer.

Examples of aromatic diamines used in the production of phenolic hydroxyl-containing polybutadiene-modified polyamidoresins include diaminobenzene, diaminotoluene, diaminophenol, and diaminodimethylbenzene. , Diamino mesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether , Diaminodimethyldiphenyl ether, methylenediamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline) ), Methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline), isopropylidene Diphenylamine, diaminobenzophenone, diaminodimethylbenzophenone, diaminoanthraquinone, diaminodiphenylsulfide, diaminodimethyldiphenylsulfide, diamine Aminodiphenylphosphonium, diaminodiphenylphosphonium, diaminophosphonium and the like. Examples of aliphatic diamines used in the production of phenolic hydroxyl-containing polybutadiene-modified polyamine resins include ethylenediamine, propylenediamine, hydroxypropylenediamine, butanediamine, heptanediamine, and hexane. Diamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, azapentanediamine, triazaundecanediamine and the like. These can be used alone or in combination of two or more.

Examples of the phenolic hydroxyl-containing dicarboxylic acid used in the production of phenolic hydroxyl-containing polybutadiene-modified polyamine resins include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, Dihydroxyisophthalic acid, dihydroxyterephthalic acid, etc. Examples of the dicarboxylic acid that does not contain a phenolic hydroxyl group used in the production of phenolic hydroxyl-containing polybutadiene-modified polyamine resins include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and carboxyl groups at both ends. Oligomers etc. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, and sulfonyl. Benzoic acid, naphthalenedicarboxylic acid, etc. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, and tartaric acid. (Meth) acrylic acid succinic acid, bis (meth) acrylic acid succinic acid, (meth) acrylic acid methoxymalic acid, (meth) acrylic acid succinic acid, (formaldehyde) Group) acrylamide malic acid and the like. These can be used alone or in combination of two or more.

Polybutadiene-modified polybutadiene resins containing phenolic hydroxyl groups can also be used in the market. Examples of commercially available products include polyamine resins "BPAM-01" and "BPAM-155" manufactured by Nippon Kayaku Co., Ltd. "Wait. From the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and an excellent bonding strength with a conductive layer formed by a plating method, the polyamide resin is preferably "BPAM-01" and "BPAM-155", and more preferably "BPAM-155". "BPAM-155" is a rubber modified polyamide resin with an amine group at the end and has reactivity with epoxy groups. Therefore, an interlayer insulating layer obtained from a thermosetting resin composition containing "BPAM-155" exists The bonding strength with the conductor layer formed by the plating method is more excellent, and the surface roughness tends to be smaller.

From the viewpoints of solubility in a solvent and film thickness retention of an auxiliary layer after lamination, the number average molecular weight of the polyamide resin is preferably 20,000 to 30,000, more preferably 22,000 to 29,000, and even more preferably 24,000 ～ 28,000. From the same viewpoint, the weight average molecular weight of the polyamide resin is preferably 100,000 to 140,000, more preferably 103,000 to 130,000, and even more preferably 105,000 to 120,000.

In the case where the resin composition for an auxiliary layer contains a polyamide resin, from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and a high adhesiveness to a conductor layer, the resin composition for an auxiliary layer is larger than that of the resin composition for an auxiliary layer. The solid content is 100 parts by mass, and the content of the polyamide resin is preferably 2 parts by mass to 15 parts by mass, more preferably 4 parts by mass to 13 parts by mass, and even more preferably 6 parts by mass to 12 parts by mass. When the content of the polyamide resin is 2 parts by mass or more, there is a tendency that the bonding strength with the conductor layer formed by the plating method is excellent. When the content is 15 parts by mass or less, the interlayer insulating layer is roughened with an oxidizing agent. In this case, the surface roughness of the interlayer insulating layer tends to be suppressed, and the reflow soldering heat resistance tends to be excellent.

[(L) Inorganic filler having a specific surface area of 20 m ² / g to 500 m ² / g] The resin composition for an auxiliary layer preferably further contains (L) a specific surface area of 20 m ² / g to 500 m ² / g of inorganic filler (hereinafter also referred to as "(L) inorganic filler"). (L) Inorganic fillers are important from the viewpoint of preventing scattering of the resin and making the shape of the laser processing uniform when laser processing is performed on the interlayer insulating layer formed by thermally curing the resin composition of the present invention. . In addition, when the surface of the interlayer insulating layer is roughened with an oxidizing agent, it is important from the viewpoint that a moderately roughened surface can be formed and a conductive layer having excellent adhesion strength can be formed by plating. Select from the viewpoints.

(L) Examples of the inorganic filler include silicon dioxide, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these compounds, silicon dioxide is preferred in terms of obtaining excellent varnish operability and low thermal expansion coefficient. (L) The inorganic filler may be used alone or in combination of two or more.

From the viewpoint of forming fine wiring, the (L) inorganic filler is preferably one having a small particle diameter. In addition, from the same viewpoint, the specific surface area of the (L) inorganic filler is 20 m ² / g to 500 m ² / g, preferably 60 m ² / g to 200 m ² / g, and more preferably 90 m ² / g to 130 m ² / g. (L) The shape of the inorganic filler is arbitrary. In particular, the fumed silica and colloidal silicon dioxide described below are not spherical. Therefore, in order to show the formation of a moderately roughened surface, and the formation of a conductive layer having excellent bonding strength. For other effects, it is preferable to adjust the specific surface area to the above range. The specific surface area can be determined by the Brunauer-Emmett-Teller (BET) method using physical adsorption at low temperature and low humidity by an inert gas such as nitrogen. Specifically, a molecule having a known adsorption area such as nitrogen can be adsorbed on the surface of the powder particle at the temperature of liquid nitrogen, and the specific surface area of the powder particle can be obtained based on the amount of adsorption.

(L) A commercially available thing can also be used for an inorganic filler. Commercially available (L) inorganic fillers include "AEROSIL (registered trademark) R972" (specific surface area of 110 ± 20 m ² / g) and "Aerosil ( AEROSIL) (registered trademark) R202 "(specific surface area 100 ± 20 m ² / g) (the above are manufactured by Japan Aerosil Co., Ltd.)," PL-1 "(specific ratio of colloidal silicon dioxide) Surface area is 181 m ² / g) and "PL-7" (specific surface area is 36 m ² / g) (the above are manufactured by Fuso Chemical Industry Co., Ltd.). In order to improve the moisture resistance, the (L) inorganic filler may be an inorganic filler that is surface-treated with a surface treatment agent such as a silane coupling agent. The (L) inorganic filler is preferably one that is dissolved or uniformly dispersed in an organic solvent.

When the resin composition for an auxiliary layer contains an (L) inorganic filler, from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and a high adhesiveness with a conductor layer, the resin composition for an auxiliary layer is more favorable. The solid content of the product is 100 parts by mass, and the content of the (L) inorganic filler is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 7 to 20 parts by mass. If the content of the (L) inorganic filler is 3 parts by mass or more, the resin can be prevented from scattering during laser processing, and the laser processing shape of the interlayer insulating layer can be adjusted. If it is 40 parts by mass or less, high plating can be obtained. Apply peel strength.

[(M) Hardening Accelerator] The resin composition for an auxiliary layer preferably further contains (M) a hardening accelerator. Examples of the (M) hardening accelerator include those similar to the (G) hardening accelerator. Among these, an organic phosphorus compound is preferable, and triphenylphosphine is more preferable. When the resin composition for the auxiliary layer contains (M) a hardening accelerator, its content also varies depending on the type of the (M) hardening accelerator. For example, when an organic phosphorus compound is contained as the (M) hardening accelerator. With respect to 100 parts by mass of the solid content of the (J) epoxy resin, it is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.1 part by mass, and even more preferably 0.003 to 0.05 part by mass.

[Other Components] Next, the resin composition for an auxiliary layer may contain components other than the above components within a range that does not inhibit the effect of the present invention. Other components include the same as other components which can be contained in the resin composition for an interlayer insulating layer.

<Manufacturing method of a multilayer resin film> The manufacturing method of the multilayer resin film of this invention is the method of apply | coating the resin composition for the auxiliary layer which forms a varnish state on a support body, and drying it, for example, and forming a bonding agent on a support body. After the auxiliary layer, a resin composition for an interlayer insulating layer in a varnished state is applied to the subsequent auxiliary layer, and then dried to form a resin composition layer for an interlayer insulating layer. Other methods include, for example, a method in which a bonding auxiliary layer is formed on a support, and a resin composition layer for an interlayer insulating layer is formed on a peelable film to form a surface having a bonding auxiliary layer. The surface of the resin composition layer for the interlayer insulation layer is formed in contact with the surface, and the adhesive auxiliary layer formed on the support is laminated with the resin composition layer for the interlayer insulation layer formed on the film. In this case, a film capable of peeling the resin composition layer for an interlayer insulating layer may also function as a protective film.

The method and drying conditions for applying and adhering the resin composition for the auxiliary layer and the resin composition for the interlayer insulating layer are the same as the methods and conditions usable in the production of the resin composition film for the interlayer insulating layer of the present invention.

[Multilayer printed wiring board] The multilayer printed wiring board of the present invention is obtained by using at least one selected from the group consisting of a resin film for an interlayer insulating layer and a multilayer resin film of the present invention. That is, the resin film for an interlayer insulating layer of the present invention is useful as a multilayer printed wiring board application. Furthermore, the resin film for an interlayer insulating layer of the present invention is useful as a multi-layer printed wiring board, particularly as a build-up layer for a build-up wiring board. The multilayer printed wiring board of the present invention can be manufactured, for example, by a manufacturing method including the following steps (1) to (6) [wherein step (3) is arbitrary], and it can also be performed in steps (1) and (2). ) Or step (3), peel or remove the support. In addition, when it abbreviates as "resin film" below, it means "resin film for interlayer insulation layers" or "multilayer resin film."

(1) A step of laminating the resin film of the present invention on one or both sides of a circuit board [hereinafter, referred to as a laminating step (1)]. (2) A step of thermally curing the resin film laminated in step (1) to form an insulating layer [hereinafter, referred to as an insulating layer forming step (2)]. (3) A step of making a hole in the circuit board on which the insulating layer is formed in step (2) [hereinafter referred to as a hole-opening step (3)]. (4) A step of roughening the surface of the insulating layer with an oxidizing agent [hereinafter, referred to as a roughening step (4)]. (5) A step of forming a conductive layer on the surface of the roughened insulating layer by plating [hereinafter, referred to as a conductive layer forming step (5)]. (6) A step of forming a circuit on a conductor layer [hereinafter, referred to as a circuit forming step (6)].

The laminating step (1) is a step of laminating the resin film of the present invention on one or both sides of a circuit board using a vacuum laminator. Examples of the vacuum laminator include: a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., and a roller dry type manufactured by Hitachi Seisakusho Co., Ltd. Coating machine, vacuum laminator manufactured by Hitachi Chemical Co., Ltd., etc.

In the case where a protective film is provided on the resin film, the protective film can be peeled off or removed, and then the resin composition layer and circuit for the interlayer insulating layer resin film of the present invention or the multilayer resin film of the present invention can be peeled off or removed. The substrates are contacted by laminating the substrates under pressure while applying pressure to the circuit substrates. This lamination can, for example, preheat the resin film and the circuit board as needed, and the compression temperature is 60 ° C to 140 ° C, and the compression pressure is 0.1 MPa to 1.1 MPa (9.8 × 10 ⁴ N / m ² ～ 107.9 × 10 ⁴ N / m ² ), and the pressure is reduced under a pressure of 20 mmHg (26.7 hPa) or less. The lamination method may be a batch method or a continuous method using a roll.

In the insulating layer forming step (2), first, the resin film laminated on the circuit substrate in the laminating step (1) is cooled to around room temperature. When the support is peeled off, after peeling, the resin film laminated on the circuit board is heated and hardened to form an insulating layer, that is, an insulating layer that becomes an "interlayer insulating layer" thereafter. When a multilayer resin film is used, the insulating layer formed here is a layer composed of a cured product of a resin composition layer for an interlayer insulating layer and a cured product of an auxiliary layer. The heat curing can be performed in two stages. For conditions, for example, the first stage is 100 ° C to 200 ° C, 5 minutes to 30 minutes, and the second stage is 140 ° C to 220 ° C, 20 minutes to 80 minutes. When using the support body which performed the mold release process, you may peel a support body after thermosetting.

After using the method to form an insulating layer, if necessary, a hole-opening step (3) may also be performed. The hole-opening step (3) is a step of forming a through-hole, a through-hole, etc. on the circuit substrate and the formed insulating layer by drilling, laser, plasma, a combination of these, and the like. The laser can be a carbon dioxide laser, a yttrium aluminum garnet (YAG) laser, an ultraviolet (UV) laser, an excimer laser, and the like.

In the roughening treatment step (4), the surface of the insulating layer is roughened by using an oxidizing agent. In addition, when via holes, through holes, and the like are formed on the insulating layer and the circuit board, the so-called "glue residue" generated at these times may be removed by an oxidizing agent. The roughening treatment and the slag removal can be performed simultaneously. Examples of the oxidant include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid, and the like. Among these, an alkaline permanganic acid solution (for example, hydroxide of potassium permanganate, sodium permanganate, etc.) which is a common oxidizing agent for roughening an insulating layer when manufacturing multilayer printed wiring boards by an additional process can be used Aqueous sodium). By roughening, an uneven anchor is formed on the surface of the insulating layer.

In the conductive layer forming step (5), a conductive layer is formed on the surface of the insulating layer of the fixture having unevenness by roughening to form a conductive layer. Examples of the plating method include an electroless plating method and an electrolytic plating method. The metal used for plating is not particularly limited as long as it can be used in plating. The metal used for the plating may be selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, and copper is preferred. , Nickel, more preferably copper. Alternatively, a method may be adopted in which a plating resist having a pattern opposite to that of the conductor layer (wiring pattern) is formed in advance, and then the conductor layer (wiring pattern) is formed only by electroless plating. After the conductor layer is formed, an annealing treatment may be performed at 150 ° C to 200 ° C for 20 minutes to 120 minutes. By performing the annealing treatment, there is a tendency that the bonding strength between the interlayer insulating layer and the conductor layer is further improved and stabilized. In addition, the annealing treatment can also promote the hardening of the interlayer insulating layer. In the circuit forming step (6), the method of forming a circuit by patterning the conductor layer can be used: subtractive color method, full addition method, semi-additive method (SAP: Semi Additive Process), and improved semi-additive method (m -SAP: Modified Semi Additive Process).

The surface of the conductor layer produced as described above may be roughened. By roughening the surface of the conductor layer, there is a tendency that the adhesiveness with the resin contacting the conductor layer is improved. For roughening the conductor layer, "CZ-8100", "CZ-8101", and "CZ-5480" (all products manufactured by Mike (MEC) Co., Ltd.) are used as organic acid-based microetchants. Wait.

Examples of the circuit board used in the multilayer printed wiring board of the present invention include glass epoxy, metal substrate, polyester substrate, polyimide substrate, and bismaleimide triazine (BT) resin. On one or both sides of a substrate such as a substrate or a thermosetting polyphenylene ether substrate, a patterned conductor layer (circuit) is formed. In addition, the circuit board in the present invention also includes a multilayer printed wiring board having a conductor layer and an insulating layer alternately formed on one or both sides with a patterned conductor layer (circuit) on one side, and one side of the circuit board. Or an interlayer insulating layer formed of the resin film of the present invention on both sides, and a patterned conductor layer (circuit) on one or both sides thereof, a hardening formed by bonding and curing the resin film of the present invention (The layer structure is the order of the auxiliary layer, the resin composition layer for the interlayer insulation layer, the resin composition layer for the interlayer insulation layer, and the order of the auxiliary layer) with a patterned conductor layer (circuit) on one or both sides Are waiting. From the viewpoint of the adhesion of the interlayer insulating layer to the circuit board, the surface of the conductor layer of the circuit board may be roughened in advance by a blackening process or the like.

[Semiconductor Package] The semiconductor package of the present invention is obtained by mounting a semiconductor on the multilayer printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor wafer, a memory, and the like at a predetermined position of the multilayer printed wiring board of the present invention. Furthermore, the semiconductor element can be sealed with a sealing resin or the like. [Example]

[1] Second, the first invention will be further described in detail through examples. The first invention is not limited to these examples.

Example 1 As an epoxy resin, 25.8 parts by mass of a biphenol novolac-type epoxy resin "NC-3000-H" (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration: 100% by mass) was used as 6.3 parts by mass of "PAPS-PN2" (made by Asahi Organic Materials Industry Co., Ltd., trade name, solid content concentration is 100% by mass, Mw / Mn = 1.17) of novolac-type phenol resin, as an epoxy resin hardener 4.9 parts by mass of triazine modified phenol novolac resin "LA-1356-60M" (manufactured by DIC Corporation, trade name, solvent: MEK, solid content concentration of 60% by mass), as an inorganic filler 92.9 parts by mass of the surface of "SO-C2" (manufactured by Admatechs Co., Ltd., trade name, average particle size: 0.5 μm) was treated with an amine silane coupling agent and dispersed in MEK Silicon dioxide (solid content concentration: 70% by mass), 0.026 parts by mass of 2-ethyl-4-methylimidazole "2E4MZ" (manufactured by Shikoku Chemical Industry Co., Ltd. as a hardening accelerator, trade name, solid Concentrated 100 mass%), and the solvent be formulated as an additional 13.1 parts by mass of MEK, and the mixing is a bead mill dispersion treatment to prepare a resin film followed by a varnish composition. The obtained resin composition varnish 1 for an adhesive film was applied to PET (manufactured by Teijin DuPont Films Co., Ltd., trade name: G2, film thickness: 50 μm) as a support film, The resin composition is dried to form a resin composition layer. The coating thickness was set to 40 μm, and drying was performed so that the residual solvent in the resin composition layer became 8.0% by mass. After drying, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-13, thickness: 25 μm) was laminated on the resin composition side as a protective film. Then, the obtained film was wound into a roll shape, and an adhesive film 1 was obtained.

Example 2 to Example 6, Example 8, Comparative Example 1 to Comparative Example 4 Except that in Example 1, the raw material composition and manufacturing conditions were changed to those described in Table 1 in the same manner as in Example 1. Thus, adhesive film 2 to adhesive film 6 and adhesive film 8 to adhesive film 12 were obtained.

Example 7 A support film 2 having a thickness of 60 μm was prepared on PET (Teijin DuPont Films Co., Ltd., a trade name: G2, film thickness: 50 μm) as a support film. The resin varnish A produced by the following procedure was applied and dried so as to have a film thickness of 10 μm.

The resin varnish A used is produced by the following procedure. 63.9 parts by mass of a biphenol novolac type epoxy resin "NC-3000-H" (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration: 100% by mass) as an epoxy resin, and as an epoxy resin 18.0 parts by mass of a triazine modified phenol novolak resin "LA-1356-60M" (manufactured by DIC Corporation, trade name, solvent: MEK, solid content concentration of 60% by mass), 15.2 "EXL-2655" (manufactured by Rohm and Haas Electronic Materials Co., Ltd., a trade name) as a core-shell rubber particle, and 8.8 parts by mass of aerosol, silicon as an inorganic filler (Aerosil) R972 "(manufactured by Japan Aerosil Co., Ltd., trade name, average particle size: 0.02 μm, solid content concentration of 100% by mass), 1.28 parts by mass of 2-B as a hardening accelerator A methyl-4-methylimidazole "2E4MZ" (manufactured by Shikoku Chemical Industry Co., Ltd., trade name, solid content concentration: 100% by mass), and 226.1 parts by mass of cyclohexanone as an additional solvent were blended and implemented The resin varnish A was prepared by mixing and dispersing the beads. The obtained resin varnish A was applied to a PET (made by Teijin DuPont Films Co., Ltd.) as a support film so as to have a film thickness of 10 μm, trade name: G2, film thickness: 50 μm), and then dried to obtain a support film 2 having a film thickness of 60 μm.

Next, under the raw material composition and manufacturing conditions shown in Table 1, the resin composition varnish for adhesive films coated on the obtained support film 2 was produced in the same manner as in Example 1. Using the support film 2 and the resin composition varnish for an adhesive film, an adhesive film 7 was obtained in the same manner as in Example 1.

[Evaluation method] The obtained adhesive films 1 to 12 were evaluated by the following methods.

(Production and Test Method of Operational Test Sample for Adhesive Film) The obtained Adhesive Film 1 to Adhesive Film 12 were cut to a size of 500 mm × 500 mm to produce Operational Test Samples 1 to Adhesive Film. Sample 12. The workability test samples 1 to 12 using the produced adhesive film were evaluated for workability by the following methods (1) to (3), and the failure in any of the tests was referred to as "operability failure". "If no defect is found in any of the tests, the" operability is good. " (1) For the samples 1 to 12 for the operability test of the adhesive film, the protective film was peeled off first. When the protective film is peeled off, a part in which the coated and dried resin adheres to the protective film side or a powder falls off is considered to have poor operability. (2) Two points at the central end of the gripping film (two points at the end so as to be 500 mm × 250 mm), and those having cracks on the coated and dried resin were regarded as having poor operability. (3) "MCL-E-679FG (R)" (made by Hitachi Chemical Co., Ltd.) is a copper-clad laminate that has been blackened and reduced on the surface of the copper foil. The thickness of the copper foil is 12 μm and the thickness is 0.41 mm. ), A batch-type vacuum pressure laminator "MVL-500" (manufactured by Meiji Seisakusho Co., Ltd., trade name) was used to laminate the layers. The vacuum degree at this time is 30 mmHg or less, the temperature is set to 90 ° C, and the pressure is set to 0.5 MPa. After cooling to room temperature, the support film was peeled (for the adhesive film 7, peeling was performed between the PET in the support film 2 and the resin layer formed thereon). At this time, a material that causes powder to fall or PET to rupture halfway is considered to have poor operability.

(Production of a sample for measuring the coefficient of thermal expansion and a test method) The obtained adhesive films 1 to 12 were cut to a size of 200 mm × 200 mm, and the protective film was peeled off and used on a copper foil having a thickness of 18 μm. A batch type vacuum pressure laminator "MVL-500" (manufactured by Meiki Seisakusho Co., Ltd., trade name) is laminated by lamination. The vacuum degree at this time is 30 mmHg or less, the temperature is set to 90 ° C, and the pressure is set to 0.5 MPa. After cooling to room temperature, the support film (the adhesive film 7 was peeled between the PET in the support film 2 and the resin layer formed thereon) was peeled and cured in a dryer at 180 ° C. for 120 minutes. Then, the copper foil was removed using a ferric chloride solution, and those having a width of 3 mm and a length of 8 mm were cut out as samples 1 to 12 for measuring the coefficient of thermal expansion.

Using the produced samples 1 to 12 for measuring the coefficient of thermal expansion, the coefficient of thermal expansion was measured by the following method. Using a thermomechanical analysis device manufactured by Seiko Instruments Co., Ltd., the obtained samples 1 to 12 for measuring the coefficient of thermal expansion were heated to 240 ° C at a heating rate of 10 ° C / min, and cooled to -10 ° C. Then, the temperature was increased to 300 ° C at a temperature increase rate of 10 ° C / min to obtain a change curve of the amount of expansion at this time, and an average thermal expansion coefficient of 0 ° C to 150 ° C of the change curve of the expansion amount was obtained.

(Production and Test Method of Embedded Evaluation Board) The inner layer circuit used in the embedded evaluation board is as follows. 5 mm on a copper-clad laminate "MCL-E-679FG (R)" (made by Hitachi Chemical Co., Ltd.) with a thickness of 12 μm and a thickness of 0.15 mm (including copper foil) A through hole having a diameter of 0.15 mm was produced at intervals and in a group of 25 × 25 pieces using a drilling method. Next, slag removal and electroless plating were performed, and electrolytic plating was performed in the through holes using electrolytic plating. As a result, a circuit board including a copper thickness of 0.2 mm, a diameter of 0.1 mm, and 25 × 25 through-holes at 5 mm intervals was obtained. Next, the adhesive films 1 to 12 from which the protective film was peeled were arranged so that the resin composition layer faced the circuit surface side of the circuit board, and then a batch type vacuum laminator "MVL-500" (named (Manufactured by Koki Seisakusho Co., Ltd., trade name) and laminated by lamination. The vacuum degree at this time was 30 mmHg, the temperature was set to 90 ° C, and the pressure was set to 0.5 MPa. After cooling to room temperature, two aluminum plates having a thickness of 1 mm were used to sandwich a circuit board with an adhesive film on both sides and a through-hole, and laminated using the vacuum laminator. The vacuum at this time was 30 mmHg, the temperature was set to 90 ° C, and the pressure was set to 0.7 MPa. After cooling to room temperature, the support film (the adhesive film 7 was peeled between the PET in the support film 2 and the resin layer formed thereon) was peeled and cured in a dryer at 180 ° C. for 120 minutes. In this way, the embedment evaluation substrates 1 to 12 were obtained.

Using the produced embedding evaluation substrates 1 to 12, the embedding properties were evaluated by the following methods. The step of the surface of the through-hole portion of the embedment evaluation substrate 1 to substrate 12 was measured using a contact surface roughness meter "SV2100" (trade name) manufactured by Mitutoyo Co., Ltd. The step was measured so as to enter the central portion of the surface of 10 through holes, and an average of 10 pits was calculated.

[Table 1]

The components of Table 1 are shown below. [Epoxy resin] ・ NC-3000-H: Biphenol novolac type epoxy resin (made by Nippon Kayaku Co., Ltd., trade name, solid content concentration is 100% by mass) ・ N-673-80M: cresol novolac Varnish-type epoxy resin (manufactured by DIC Corporation, trade name, solvent: MEK, solid content concentration of 80% by mass) [Novolac-type phenol resin] ・ PAPS-PN2: Novolac-type phenol resin (Asahi Manufactured by Organic Materials Industry Co., Ltd., trade name, solid content concentration is 100% by mass, Mw / Mn = 1.17) ・ PAPS-PN3: Novolac phenol resin (Manufactured by Asahi Organic Materials Industry Co., Ltd., trade name, solid contents Concentration is 100% by mass, Mw / Mn = 1.50) • HP-850: Novolac-type phenol resin manufactured by using hydrochloric acid instead of phosphoric acid (manufactured by Hitachi Chemical Co., Ltd., trade name, solid content concentration is 100% by mass ) [Triazine-modified phenol novolac resin] • LA-1356-60M: Triazine-modified phenol novolac resin (manufactured by DIC), trade name, solvent: MEK, solid content concentration is 60 mass %) [ Inorganic fillers] ・ SO-C2: The surface of silicon dioxide "SO-C2" (trade name, average particle size: 0.5 μm) manufactured by Admatechs Co., Ltd. is made with an amine silane coupling agent Processed and dispersed in MEK solvent (solid content concentration: 70% by mass). • SO-C6: "SO-C6" (trade name) manufactured by Admatechs Co., Ltd. , Average particle size: 2.2 μm) The surface is treated with an amine silane coupling agent, and then dispersed in MEK solvent (solid content concentration of 70% by mass). • Aerosil R972: Fumed Silica (Manufactured by Japan Aerosil Co., Ltd., trade name, solid content concentration is 100% by mass, specific surface area: 100 m ² / g) [hardening accelerator] ・ 2E4MZ: 2-ethyl-4-formaldehyde Kimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name, solid content concentration is 100% by mass)

As can be seen from Table 1, the adhesive film of the present invention has good operability, and an interlayer insulating layer having a low thermal expansion coefficient and excellent embedding properties can be obtained from the adhesive film of the present invention. On the other hand, when the adhesive film of the present invention is not used, any of the operability, the coefficient of thermal expansion, and the embedding property are deteriorated. That is, it was found that according to the first invention, an adhesive film having a low thermal expansion coefficient, excellent embedding properties, and excellent handleability can be provided, and an interlayer insulating layer having a low thermal expansion coefficient after curing can be provided.

[2] Next, the second invention will be described in detail, but the second invention is not limited to these examples.

The weight-average molecular weight of the cyanate ester prepolymer, the weight-average molecular weight of the polyamide resin, and the number-average molecular weight were determined by gel permeation chromatography (GPC) conversion from a calibration curve using standard polystyrene. The standard curve is a standard polystyrene: TSKgel (SuperHZ2000, SuperHZ3000 [manufactured by Tosoh Corporation]), and is approximated by a cubic equation. The conditions of GPC are shown below.・ Device: Pump: 880-PU [manufactured by JASCO Corporation] RI detector: 830-RI [manufactured by JASCO Corporation] Thermostat: 860-CO [manufactured by JASCO Corporation] Automatic sampler: AS -8020 [manufactured by Tosoh Corporation] • Eluent: Tetrahydrofuran • Sample concentration: 30 mg / 5 mL • Injection volume: 20 μL • Flow rate: 1.00 mL / min • Measurement temperature: 40 ° C

[Synthesis of cyanate ester prepolymer] Production Example 1 (Synthesis of cyanate ester prepolymer A) A 5 liter of polymer having a Dean-Stark reflux cooler, a thermometer, and a stirrer was used. In a separate flask, 3,000 g of "AroCy (registered trademark) B-10" (Hens) as a bisphenol A-type difunctional cyanate resin (bisphenol A-type dicyanate resin) was introduced. As a reaction solution, 45.8 g of p- (α-cumyl) phenol (manufactured by Mitsui Fine Chemicals Co., Ltd., with a molecular weight of 212) and 1,303 g of toluene manufactured by Huntsman were used as a reaction solution. The temperature rise of the reaction solution was started, and it stirred until the temperature of the reaction solution became 90 degreeC. When the temperature reached 90 ° C, 2.799 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration: 8% by mass, cut product of mineral spirit solution) was added to the reaction solution. Then, it heated up to 110 degreeC, and stirred at 110 degreeC for 180 minutes. Next, by adding toluene so that the solid content concentration of the reaction solution becomes 70% by mass, a cyanate ester prepolymer A (weight average molecular weight: about 3,200) dissolved in toluene is prepared.

[Preparation of a Supporting Adhesive Layer with a Support] Production Example 2 According to the blending composition shown in Table 2 (the values in the table are parts by mass of solid content, in the case of a solution (other than an organic solvent) or a dispersion liquid: A solid content conversion amount) The composition was prepared, stirred until the resin component was dissolved, and dispersed by a bead mill treatment, thereby obtaining a varnish-like resin composition for an auxiliary layer (solid content concentration: 20% by mass). Using a die coater, the obtained resin composition for an auxiliary layer was applied to a 38 μm-thick PET film (Teijin DuPont Films Co., Ltd.) that had been subjected to a release treatment on one side as a support. Co., Ltd., NR-1 (product name), the release-treated surface was dried at 130 ° C. for 2 minutes to obtain an adhesive auxiliary layer with a support having a thickness of 3 μm and an auxiliary layer. The raw materials used are shown in Table 2.

[Table 2]

The materials used for the preparation of the resin varnish for the auxiliary layer are shown below.

[(H) Cyanate Resin]-Cyanate Prepolymer A: Cyanate Prepolymer A synthesized in Production Example 1

[(J) Epoxy resin]-NC-3000-H: Novolac epoxy resin containing biphenylaralkyl structure ("NC-3000-H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 289 g / eq, solid content concentration is 100% by mass)

[(K) Polyamidoresin] BPAM-155: Modified polyamidoresin with a amine group at the end so that the solid content concentration becomes 10% by mass ("BPAM manufactured by Nippon Kayaku Co., Ltd." -155 ", number-average molecular weight: 26,000, weight-average molecular weight: 110,000, and solid content concentration of 100% by mass) were previously dissolved in dimethylacetamide.

[(L) Inorganic Filling Materials] ・ Aerosil R972: Fumed Silicon ("Aerosil (registered trademark) R972" manufactured by Japan Aerosil Corporation) Surface area: 100 m ² / g, solid content concentration is 100% by mass)

[(M) Hardening accelerator] • TPP: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd., solid content concentration is 100% by mass)

[Chemical 18]

[Production of Resin Film for Interlayer Insulation Layer] Example 1 According to the blending composition shown in Table 3 (the values in the table are parts by mass of solid content, and in the case of a solution (other than an organic solvent) or a dispersion liquid, the solid content is Conversion amount) The composition was prepared and dispersed by a bead mill treatment to obtain a varnish-like resin composition 1 for an interlayer insulating layer (solid content concentration: 72% by mass). Next, using a die coater, the resin composition 1 for an interlayer insulating layer was applied to a 38 μm-thick PET film that had been demolded on one side as a support (Teijin DuPont Films Co., Ltd. The mold release surface (manufactured by the company, NR-1, product name) was dried at 100 ° C for 1.5 minutes to obtain a resin film for an interlayer insulating layer having a film thickness of 40 μm on a PET film.

Example 2 to Example 9, Example 11 to Example 12, Comparative Example 1 Except that in Example 1, the composition of the resin composition for an interlayer insulating layer was changed to the composition shown in Table 3, and it was the same as the example. 1A resin film for an interlayer insulating layer was obtained in the same manner.

Example 10 In the same procedure as in Example 1, a resin composition 1 for an interlayer insulating layer was obtained. Next, using a die coater, the resin composition 1 for an interlayer insulating layer was applied to the bonding auxiliary layer (thickness: 3 μm) with the supporting bonding layer and the supporting layer obtained in Production Example 2 and dried at 100 ° C. In 1.5 minutes, a resin composition layer for an interlayer insulating layer having a film thickness of 37 μm was formed thereby to obtain a multilayer resin film.

The obtained interlayer insulating layer resin film and the multilayer resin film (hereinafter, these are also simply referred to as "resin films") were evaluated according to the following evaluation methods. The results are shown in Table 3.

[Evaluation method] (1) Glass transition temperature (Tg) (evaluation of heat resistance) The glass transition temperature (Tg) is a sheet-shaped hardened body made of the resin film obtained in each example, and the hardened body is subjected to thermomechanical analysis ( TMA). The sheet-like hardened body is produced by laminating one piece of a laminated resin film to produce a laminated body of a total of five pieces, and heat-hardening the laminated body at 190 ° C. for 180 minutes. The cured substrate was cut into a length of 40 mm (X direction), a width of 4 mm (Y direction), and a thickness of 80 mm (Z direction) as an evaluation substrate. A thermomechanical analysis device (TA instrument) was used for the evaluation substrate. (Manufactured by TA Instruments), Q400), and the thermomechanical analysis was performed by the compression method. Specifically, after the evaluation substrate was mounted on the device in a stretching direction (xy direction), the measurement was performed twice under a measurement condition of a load of 5 g and a temperature increase rate of 10 ° C./min, and a second measurement was determined. The Tg shown in the intersections of different wires in the thermal expansion curve is used as an index of heat resistance.

(2) Dielectric loss tangent (evaluation of electrical characteristics) A sheet-like cured product was produced by the same method as the method for producing a cured product of a resin film used for evaluation of glass transition temperature, and the cured product was cut to a length of 70 mm and 2 mm width were used as evaluation samples. For this evaluation sample, the dielectric loss tangent was measured at a measurement frequency of 5 GHz and a measurement temperature of 23 ° C by using a cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies.

(3) Evaluation of operability After the resin film obtained in each example was left at room temperature (25 ° C) for 5 days, the resin surface was set to the outside (the support was set to the inside) and bent at 180 ° to The presence or absence of cracking was visually confirmed. Twenty resin films were confirmed and shown in Table 3 in the form of "the number of resin films having cracks / 20".

(4) Gel time storage rate (evaluation of storage stability) The gel time storage rate was measured by the following methods (i) to (iii). (I) Measurement of gelation time (gelation time 1) before storage Only the resin composition was taken out from the support of the resin film obtained in each example. This resin composition was put into a gelation tester (manufactured by Nisshin Chemical Research Institute Co., Ltd.) made of a SUS plate set at 180 ° C, and was stirred using a bamboo skewer at a pace of 1 second and 2 revolutions to measure the gel Gelation time 1. (Ii) Measurement of gelation time (gelation time 2) after storage The resin film obtained in each example was stored at 5 ° C for 30 days and then taken out and returned to room temperature. Then, only the resin composition was taken out from the support of the resin film. About the obtained resin composition, the gelation time 2 was measured by the same method as the gelation time 1. (Iii) Calculation of gelatinization time storage rate From gelation time 1 and gelation time 2, the gelation time storage rate was calculated according to the following formula. Storage rate of gelation time (%) = (gelation time 2 / gelation time 1) x 100 The larger the storage rate of the gelation time, the better the storage stability.

[table 3] * 1: It means the mass part with respect to 100 mass parts of (B) cyanate resin. * 2: Equivalent ratio (active ester group / epoxy group) of the active ester group derived from the (F) active ester hardener to the epoxy group derived from the (A) epoxy resin.

Each component of Table 3 is shown below.

[(A) Epoxy resin]-N-673: Cresol novolac epoxy resin ("Epiclon (registered trademark) N-673" manufactured by DIC Corporation), epoxy resin Equivalent: 210 g / eq, solid content concentration is 100% by mass) • jER157S70: bisphenol A novolac epoxy resin ("jER (registered trademark) 157S70" manufactured by Mitsubishi Chemical Co., Ltd., epoxy Equivalent: 210 g / eq, solid content concentration is 100% by mass) • jER828: bisphenol A type liquid epoxy resin ("jER (registered trademark) 828" manufactured by Mitsubishi Chemical Co., Ltd., solid Component concentration is 100% by mass, epoxy equivalent: 185 g / eq)

[(B) Cyanate resin] • Cyanate prepolymer A: Cyanate prepolymer A synthesized in Production Example 1 • BA230S: Prepolymer of bisphenol A type cyanate resin (Lonza ( (Lonza) "Primaset BA230S") ・ BA3000S: Prepolymer of bisphenol A type cyanate resin ("Primaset BA3000S" manufactured by Lonza) )

[(C) Inorganic Filler] ・ Amine-based silane coupling agent treated SO-C2: Amine-based silane coupling agent will be used so that the solid content concentration becomes 70% by mass (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM573) Treated spherical silica "SO-C2" (manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm) dispersed in MEK solvent.

[(D) Monofunctional phenol compound]-p- (α-cumyl) phenol: manufactured by Kanto Chemical Co., Ltd. 4- (benzyloxy) phenol: manufactured by Tokyo Chemical Industry Co., Ltd. 2,3,6-tri Methylphenol: manufactured by Honshu Chemical Industry Co., Ltd.

[(E) Phenoxy resin] • YX7200B35: phenoxy resin ("jER (registered trademark) YX7200B35" manufactured by Mitsubishi Chemical) Co., Ltd., epoxy equivalent: 3,000 g / eq to 16,000 g / eq , Solid content concentration is 35% by mass, MEK cut product)

[(F) Active ester hardener] ・ HPC-8000-65T: Active ester resin ("EPICLON (registered trademark) HPC-8000-65T" manufactured by DIC Corporation), solid content 65% by mass, toluene cut product)

[(G) Hardening accelerator] • TPP: Triphenylphosphine (manufactured by Kanto Chemical Co., Ltd.) • Hardening accelerator 1: The following formula (G-7) synthesized by referring to Japanese Patent Laid-Open No. 2011-179008 Addition reaction product of tributylphosphine and 1,4-benzoquinone (solid content concentration is 100% by mass)

[Chemical 19]

・ Zinc naphthenate: (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration is 8% by mass, mineral spirit solution)

From the results in Table 3, it can be seen that the interlayer insulating layer formed by using the interlayer insulating layer resin films obtained in Examples 1 to 12 has a high glass transition temperature, a low dielectric loss tangent, and a gel time preservation ratio. And the operability is also excellent. That is, the resin film for an interlayer insulating layer of the present invention is excellent in storage stability and operability, and the interlayer insulating layer formed by the resin film for an interlayer insulating layer of the present invention is excellent in electrical characteristics and heat resistance. On the other hand, the resin film for an interlayer insulating layer of Comparative Example 1 which did not contain (D) a monofunctional phenol compound was inferior in workability, and also inferior in storage stability (gel time preservation ratio) and electrical characteristics (dielectric loss tangent).

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Claims (1)

An adhesive film for a multilayer printed wiring board includes a resin composition layer formed by forming the following resin composition on a support film. The resin composition includes: (a) a novolac phenol resin, The dispersion ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.05 to 1.8; (b) an epoxy resin represented by the following general formula (I); and (c) an inorganic filler And the average particle diameter of the (c) inorganic filler in the resin composition layer is 0.1 μm or more, and the content of the (c) inorganic filler is 20% to 95% by mass of the resin solid content , (In the formula, p represents an integer of 1 to 5.)