JP2017147422A - Adhesive film for multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film for a multilayer printed wiring board, which is superior in the property of filling irregularities even when a silica filler is highly filled.SOLUTION: An adhesive film for a multilayer printed wiring board comprises a resin composition layer arranged by forming, on a support film, a layer of a resin composition including (A) a novolac type phenol resin which is 1.1-1.7 in the variance ratio (Mw/Mn) of a weight-average molecular weight (Mw) to a number average molecular weight (Mn), (B) an epoxy resin, (C) an inorganic filler and (D) a solvent. In the adhesive film, (B) the epoxy resin is at least one novolac type epoxy resin selected from a group consisting of a novolac type epoxy resin having a biphenyl skeleton, a cresol novolac type epoxy resin and an aralkyl novolac type epoxy resin; and (C) the inorganic filler is 0.1 μm or larger in average particle diameter, of which the content in the resin composition layer is 20-95 mass% of resin solid contents, and the content of (D) the solvent in the resin composition layer is 1-20 mass%.SELECTED DRAWING: None

Description

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

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

  Organic insulating resins used in the build-up method include aromatic epoxy resins and curing agents having active hydrogen for the epoxy resins (for example, phenolic curing agents, amine curing agents, carboxylic acid curing agents, etc.) The combination of and has been mainly used. Although the cured product obtained by curing using these curing agents is excellent in the balance of physical properties, the reaction between the epoxy group and active hydrogen generates a highly polar hydroxy group, thereby increasing the water absorption rate. There has been a problem in that electrical characteristics such as dielectric constant and dielectric loss tangent are deteriorated.

  A cured product of a resin composition containing a cyanate resin and an epoxy resin has a low relative dielectric constant and dielectric loss tangent, and it is known that an organic insulating resin layer having excellent electrical characteristics can be obtained by using the resin composition. Yes. On the other hand, when an organic insulating resin layer obtained using a cyanate resin is subjected to a high-temperature and high-humidity accelerated test, the adhesive retention at the interface between the inner layer pattern and the organic insulating resin layer tends to be greatly reduced. Therefore, for example, in Patent Document 1, by using an excessive amount of the epoxy resin with respect to the cyanate resin, a decrease in the adhesive retention rate is reduced, and an active ester curing agent is used as a curing agent. This prevents a decrease in electrical characteristics due to an increase in the ratio of.

  By the way, in patent document 2, after laminating | stacking the adhesive film which consists of a support body which has a mold release layer, and an organic insulating resin layer on a core board | substrate, it thermosets in the state with a support body, and a support body remains attached. Alternatively, a method of making a hole with a laser or a drill after peeling the support is disclosed.

  In addition, the build-up layer is required to have a low thermal expansion coefficient (low CTE) due to demands for processing dimensional stability and reduction of warpage after semiconductor mounting, and efforts are being made to reduce the CTE. (For example, see Patent Documents 3 to 5). As the most mainstream method, many build-up layers have a low CTE by increasing the amount of silica filler (for example, 40 mass% or more in the build-up layer is a silica filler).

Japanese Patent No. 5556222 International Publication No. 2009/035071 JP-T-2006-527920 JP 2007-87982 A JP 2009-280758 A

[1] When the silica filler is increased in order to reduce the CTE of the build-up layer, it tends to be difficult to bury the unevenness of the wiring pattern of the inner layer circuit by the build-up material. In addition, it is required to embed an inner layer circuit such as a through hole so that unevenness is reduced by a build-up material. If the silica filler is highly filled in order to reduce the CTE of the build-up material, it tends to be difficult to satisfy these requirements.

  The first invention was made to solve such a problem, and an object of the invention is to provide an adhesive film for a multilayer printed wiring board that is excellent in unevenness embedding even when the silica filler is highly filled. To do.

[2] Although the technique of Patent Document 2 has the effect that a good blind via can be formed in an insulating layer using a carbon dioxide gas laser, an organic insulating resin comprising a cyanate resin, an epoxy resin and an active ester resin When a layer is laminated on a core substrate and cured with a support, peeling occurs at the interface between the core substrate and the organic insulating resin layer after curing, and a cured substrate with a good appearance cannot be obtained. It has become.

  The second invention has been made to solve such a problem, an interlayer insulating layer having a good appearance even when cured with a support is obtained, and the dielectric tangent of the obtained interlayer insulating layer is low, It aims at providing the resin composition excellent in the smear removal property and heat resistance after laser processing, the resin film for interlayer insulation layers using this resin composition, and a multilayer printed wiring board.

[1] As a result of intensive studies to solve the first problem, the inventors of the present invention have a resin composition containing a specific novolac-type phenolic resin, a specific epoxy resin, and a specific inorganic filler. The inventors have found that the first problem can be solved by using an object, and have completed the present invention. That is, the first invention provides the following adhesive film.

(1) (A) A novolak type phenol resin having a dispersion ratio (Mw / Mn) of 1.1 to 1.7 of a weight average molecular weight (Mw) and a number average molecular weight (Mn), and (B) an epoxy resin And (C) an inorganic filler, and (D) a solvent, and a resin composition layer formed by forming a layer on a support film, and (B) an epoxy resin has a biphenyl skeleton. At least one novolak epoxy resin selected from the group consisting of a novolak epoxy resin, a cresol novolac epoxy resin and an aralkyl novolac epoxy resin having an average particle size of (C) an inorganic filler having an average particle size of 0.1 μm or more In the multilayer composition, the content in the resin composition layer is 20 to 95% by mass of the resin solid content, and the content of the solvent (D) in the resin composition layer is 1 to 20% by mass. The adhesive film for cement wiring board.

[2] As a result of intensive studies to solve the second problem, the present inventors have found that the resin contains an epoxy resin, a cyanate resin, an active ester curing agent, a phosphorus curing accelerator, and an inorganic filler. It has been found that the second problem can be solved by using the composition, and the present invention has been completed. That is, the second invention provides the following (2) to (19).

(2) A resin composition comprising (a) an epoxy resin, (b) a cyanate resin, (c) an active ester curing agent, (d) a phosphorus-based curing accelerator, and (e) an inorganic filler.
(3) The resin composition according to (2), wherein (d) the phosphorus-based curing accelerator is an addition reaction product of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound.
(4) The above (2), wherein (d) the phosphorus curing accelerator is an addition reaction product of a phosphine compound represented by the following general formula (I) and a quinone compound represented by the following general formula (II) Or the resin composition as described in (3).

(In general formula (I), R ₁ represents an alkyl group having 1 to 12 carbon atoms, and R ₂ and R ₃ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In (II), R _{4 to} R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ₄ and R ₅ may be bonded to each other to form a cyclic structure. )
(5) Said (2)-(4) whose content of (d) phosphorus hardening accelerator is 0.01-0.5 mass part with respect to 100 mass parts of solid content conversion of a resin composition. The resin composition in any one of.
(6) The content of the epoxy resin is 5 to 60 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition, (b) the content of the cyanate resin is 2 to 50 parts by mass, (c) Resin composition in any one of said (2)-(5) whose content of an active ester hardening | curing agent is 2-30 mass parts and whose content of (e) inorganic filler is 40-85 mass parts.
(7) The resin composition according to any one of (2) to (6), further comprising (f) dicyandiamide.
(8) The resin composition according to any one of (2) to (7), further comprising (g) a phenoxy resin.
(9) (e) The above-mentioned (2) to (e), wherein the inorganic filler is surface-treated with one or more kinds of surface treatment agents selected from vinyl silane coupling agents, epoxy silane coupling agents and aminosilane coupling agents. (8) The resin composition in any one of.
(10) The resin composition according to any one of (2) to (9), further comprising (h) a resin having a siloxane skeleton.
(11) The resin composition according to any one of (2) to (10), wherein the volume average particle diameter of the inorganic filler (0.05) is 0.05 to 3 μm.
(12) A resin film for an interlayer insulating layer having a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order,
The resin film for interlayer insulation layers whose resin composition layer for interlayer insulation layers is a layer containing the resin composition in any one of said (2)-(11).
(13) The resin film for an interlayer insulation layer according to (12), wherein the adhesion auxiliary layer contains a resin composition for an adhesion auxiliary layer containing (i) an epoxy resin and (j) a cyanate resin.
(14) The resin film for an interlayer insulating layer according to (13), wherein (j) the cyanate resin is a prepolymer of a dicyanate compound having two cyanate groups in one molecule.
(15) The resin film for an interlayer insulating layer according to the above (13) or (14), wherein the resin composition for an adhesion auxiliary layer contains (k) an inorganic filler having a specific surface area of 20 m ² / g or more.
(16) The resin film for an interlayer insulating layer according to any one of (13) to (15), wherein the resin composition for an adhesion auxiliary layer contains (m) a polyamide resin containing a polybutadiene skeleton.
(17) The resin film for an interlayer insulating layer according to any one of (13) to (16), wherein the resin composition for an adhesion auxiliary layer contains (n) a phenoxy resin.
(18) The thickness of the adhesion auxiliary layer is 1 to 15 μm, the thickness of the resin composition layer for the interlayer insulating layer is 10 to 100 μm, and the thickness of the support is 10 to 150 μm. (17) The resin film for interlayer insulation layers according to any one of the above.
(19) The cured product of the resin composition according to any one of (2) to (11) or the cured product of the resin film for an interlayer insulating layer according to any one of (12) to (18), Multilayer printed wiring board.

[1] According to the first invention, it is possible to provide an adhesive film for a multilayer printed wiring board that is excellent in unevenness embedding even when the silica filler is highly filled.

[2] According to the second invention, an interlayer insulating layer having a good appearance even when cured with a support is obtained, the dielectric tangent of the obtained interlayer insulating layer is low, smear removability and heat resistance after laser processing It is possible to provide an excellent resin composition, a resin film for an interlayer insulating layer using the resin composition, and a multilayer printed wiring board.

[1] First Invention The adhesive film for a multilayer printed wiring board of the present invention has a dispersion ratio (Mw / Mn) of (A) weight average molecular weight (Mw) and number average molecular weight (Mn) of 1.1. -1.7 novolak-type phenol resin (hereinafter also referred to simply as "(A) novolak-type phenol resin"), (B) an epoxy resin, (C) an inorganic filler, and (D) a solvent. A novolak having a resin composition layer formed by forming a resin composition (hereinafter also referred to as “resin composition for an adhesive film”) on a support film, and (B) an epoxy resin having a biphenyl skeleton Type epoxy resin, cresol novolac type epoxy resin and aralkyl novolac type epoxy resin, at least one kind of novolac type epoxy resin, and (C) the average particle size of the inorganic filler is 0. 1 μm or more, the content in the resin composition layer is 20 to 95 mass% in the resin solid content, and the content of the solvent (D) in the resin composition layer is 1 to 20 mass%. It is an adhesive film for multilayer printed wiring boards.

[Resin composition for adhesive film]
The resin composition for adhesive films contains (A) a novolak-type phenol resin, (B) an epoxy resin, (C) an inorganic filler, and (D) a solvent. Hereinafter, each of these components will be described.

<(A) Novolac type phenolic resin>
(A) The novolak-type phenol resin is used as a curing agent for an epoxy resin, and the dispersion ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 1.1 to 1. .7 range.

Such (A) novolac type phenolic resin can be produced by, for example, the production method described in Japanese Patent No. 4283773.
That is, a phenol compound and an aldehyde compound as raw materials, a phosphoric acid compound as an acid catalyst, a non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent, and the two-layer separation state formed from these are subjected to, for example, mechanical stirring, Stir and mix by sonic waves, etc. to advance the reaction between the phenolic compound and the aldehyde compound as a cloudy heterogeneous reaction system (phase separation reaction) in which two layers (organic phase and aqueous phase) intermingle, and condensate (resin ) Can be synthesized.
Next, for example, a water-insoluble organic solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, etc.) is added and mixed to dissolve the condensate, and the mixing is stopped and allowed to stand, and the organic phase (organic solvent phase) and (A) Novolak by separating into an aqueous phase (phosphoric acid aqueous solution phase) and removing the aqueous phase for recovery, while the organic phase is washed with hot water and / or neutralized and then the organic solvent is recovered by distillation. Type phenolic resin can be produced.
Since the above-described method for producing a novolak-type phenolic resin utilizes a phase separation reaction, the stirring efficiency is extremely important, and it is a reaction to increase the surface area of the interface as much as possible by miniaturizing both phases in the reaction system. Desirable from an efficiency standpoint, this facilitates the conversion of phenolic compounds to resins.

Examples of the phenol compound used as the raw material include phenol, orthocresol, metacresol, paracresol, xylenol, bisphenol compound, ortho substitution having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 10 carbon atoms in the ortho position. Examples thereof include a phenol compound and a para-substituted phenol compound having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 18 carbon atoms, in the para position. You may use these individually or in mixture of 2 or more types.
Here, 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-sec-butylphenol, 2-tert-butylphenol, 2-phenylphenol, 2-cyclohexylphenol, 2-nonylphenol, 2-naphthylphenol, and the like. Is mentioned.
Examples of the para-substituted phenol compound include 4-propylphenol, 4-isopropylphenol, 4-sec-butylphenol, 4-tert-butylphenol, 4-phenylphenol, 4-cyclohexylphenol, 4-nonylphenol, 4-naphthylphenol, 4-dodecylphenol, 4-octadecylphenol, etc. are mentioned.

  Examples of the aldehyde compound used as a raw material include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, paraaldehyde, propionaldehyde, and the like. Among these, paraformaldehyde is preferable from the viewpoint of reaction rate. You may use these individually or in mixture of 2 or more types.

  The compounding 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, still more preferably 0.50 to 0.00. 90. By setting the blending molar ratio (F / P) within the above range, an excellent yield can be obtained.

The phosphoric acid compound used as the acid catalyst plays an important role in forming a phase separation reaction field with the phenol compound in the presence of water. As a phosphoric acid compound, aqueous solution types, such as 89 mass% phosphoric acid and 75 mass% phosphoric acid, can be used, for example. Moreover, you may use polyphosphoric acid, anhydrous phosphoric acid, etc. as needed.
From the viewpoint of controlling the phase separation effect, the content of the phosphate compound is, for example, 5 parts by mass or more, preferably 25 parts by mass or more, more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the phenol compound. . In addition, when using 70 mass parts or more of phosphoric acid compounds, it is preferable to ensure safety by suppressing heat generation at the initial stage of the reaction by splitting into the reaction system.

The non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent plays a very important role in promoting the phase separation reaction. As the reaction auxiliary solvent, it is preferable to use at least one compound selected from the group consisting of alcohol compounds, polyhydric alcohol ethers, cyclic ether compounds, polyhydric alcohol esters, ketone compounds, and sulfoxide compounds.
Examples of alcohol compounds include monohydric alcohols such as methanol, ethanol, and propanol, butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol. And dihydric alcohols such as polyethylene glycol and trihydric alcohols such as glycerin.
Examples of polyhydric alcohol ethers 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, ethylene glycol ethyl methyl ether, and ethylene glycol. A glycol ether etc. are mentioned.
Examples of the cyclic ether compound include 1,3-dioxane and 1,4-dioxane, and examples of the polyhydric alcohol 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”), and methyl isobutyl ketone. Examples of the sulfoxide compound include dimethyl sulfoxide and diethyl sulfoxide.
Among these, ethylene glycol monomethyl ether, polyethylene glycol, and 1,4-dioxane are preferable.
The reaction auxiliary solvent is not limited to the above examples, and may be a solid as long as it has the above-mentioned characteristics and exhibits a liquid state at the time of reaction, each being used alone or in combination of two or more. May be.
Although it does not specifically limit as a compounding quantity of a reaction auxiliary solvent, For example, it is 5 mass parts or more with respect to 100 mass parts of phenolic compounds, Preferably it is 10-200 mass parts.

By further using a surfactant during the heterogeneous reaction step, 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, alpha olefin sulfonate, alkylbenzene sulfonic acid and its salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, phenyl ether ester salt, polyoxyethylene alkyl ether sulfate ester salt, ether sulfone. Anionic surfactants such as acid salts and ether carboxylates; polyoxyethylene alkylphenyl ethers, polyoxyalkylene alkyl ethers, polyoxyethylene styrenated phenol ethers, polyoxyethylene alkylamino ethers, polyethylene glycol aliphatic esters, fats Monoglyceride, sorbitan aliphatic ester, pentaerythritol aliphatic ester, polyoxyethylene polypropylene glycol, aliphatic alkylol ama Nonionic surfactants such as de; monoalkyl ammonium chloride, dialkyl ammonium chloride, and cationic surfactants such as amine salt compounds.
Although the compounding quantity of surfactant is not specifically limited, For example, it is 0.5 mass part or more with respect to 100 mass parts of phenolic compounds, Preferably it is 1-10 mass parts.

  The amount of water in the reaction system affects the phase separation effect and production efficiency, but is generally 40% by mass or less on a mass basis. By making the amount of water 40% by mass or less, the production efficiency can be kept good.

  The reaction temperature between the phenol compound and the aldehyde compound varies depending on the type of phenol compound, reaction conditions, and the like, and is not particularly limited, but is generally 40 ° C. or higher, preferably 80 ° C. to reflux temperature, more preferably 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 blending amount of phosphoric acid, the water content in the reaction system, etc., but is generally about 1 to 10 hours.

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

(A) Novolak type phenol resin having a dispersion ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1.1 to 1.7 by the method for producing (A) novolak type phenol resin Can be manufactured.
Although different depending on the type of the phenol compound, for example, the following (A) novolac type phenol resin can be obtained depending on the range of the blending molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P).
When the blending molar ratio (F / P) is in the range of 0.33 or more and less than 0.80, the content of the monomer component of the phenol compound is, for example, 3 by gel permeation chromatography (GPC) area method. The content of the dimer component of the phenol compound is, for example, 5 to 95% by mass, preferably 10 to 95% by mass, and further the weight average molecular weight (Mw by GPC measurement). ) And the number average molecular weight (Mn), a novolac phenol resin having a dispersion ratio (Mw / Mn) of 1.1 to 1.7 can be produced in a high yield.

  (A) As a novolak-type phenol resin, a commercial item can be used, for example, "PAPS-PN2" (Asahi Organic Materials Co., Ltd. make, brand name), "PAPS-PN3" (Asahi Organic Materials Co., Ltd. stock) Company name, product name) and the like.

The resin composition for an adhesive film may be used in combination with (A) an epoxy resin curing agent other than the novolak-type phenol resin (hereinafter also simply referred to as “epoxy resin curing agent”) as long as the effects of the present invention are not impaired. .
As an epoxy resin hardening | curing agent, (A) Various phenol resin compounds other than a novolak-type phenol resin, an acid anhydride compound, an amine compound, a hydragit compound etc. are mentioned, for example. Examples of the phenol resin compound include (A) novolak type phenol resins other than the novolak type phenol resin, resol type phenol resin, and the like, and examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylic dianhydride, and the like. Products, methyl hymic acid and the like. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane, and guanylurea.

Among these epoxy resin curing agents, from the viewpoint of improving reliability, (A) novolac type phenol resins other than novolac type phenol resins are preferable.
Further, 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 novolak type phenol resin and dicyandiamide are preferable.
(A) A novolak-type phenol resin other than the novolak-type phenol resin may be a commercially available product. For example, a phenol novolak resin such as “TD2090” (manufactured by DIC Corporation, trade name), “KA-1165” (DIC) Cresol novolac resins such as those manufactured by Co., Ltd. Moreover, as a commercial item of a triazine ring containing novolak type phenol resin, for example, “Phenolite LA-1356” (manufactured by DIC Corporation, trade name), “Phenolite LA7050 series” (manufactured by DIC Corporation, trade name), etc. Examples of commercially available products of triazine-containing cresol novolak resins include “Phenolite LA-3018” (trade name, manufactured by DIC Corporation).

<(B) Epoxy resin>
(B) The epoxy resin is at least one type of novolak epoxy resin selected from the group consisting of a novolak type epoxy resin having a biphenyl skeleton, a cresol novolak type epoxy resin, and an aralkyl novolak type epoxy resin.
The 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 the molecule, and examples thereof include an epoxy resin represented by the following formula (1). You may use these individually or in mixture of 2 or more types.

  (In the formula, p represents an integer of 1 to 5.)

(B) A commercially available product may be used as the epoxy resin. Examples of commercially available (B) epoxy resins include “NC-3000” (epoxy resin having p of 1.7 in formula (1)) and “NC-3000-H” (p in formula (1) 2.8 epoxy resin) (all manufactured by Nippon Kayaku Co., Ltd., trade name) and the like.
The resin composition for an adhesive film may contain (B) an epoxy resin other than the epoxy resin, a polymer type epoxy resin such as a phenoxy resin, and the like as long as the effects of the present invention are not impaired.

<Curing accelerator>
The resin composition for adhesive films may contain a curing accelerator from the viewpoint of accelerating the reaction between (A) the novolak type phenol resin and (B) the epoxy resin. Examples of the curing accelerator include imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate; organophosphorus compounds such as triphenylphosphine; phosphonium borate Onium salts; amines such as 1,8-diazabicycloundecene; 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like. You may use these individually or in mixture of 2 or more types.

<(C) Inorganic filler>
The resin composition for adhesive films includes (C) an inorganic filler having an average particle size of 0.1 μm or more.
(C) Examples of inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and titanium. Examples thereof include barium acid, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. You may use these individually or in mixture of 2 or more types. Among these, silica is preferable from the viewpoint of lowering the thermal expansion coefficient of the interlayer insulating layer formed by curing the adhesive film.
(C) The shape of the inorganic filler is not particularly limited, but is preferably a spherical shape from the viewpoint of facilitating embedding of the through holes and circuit patterns formed in the inner layer circuit.

(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.
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 in terms of solid content from the viewpoint of embedding properties, and the average particle diameter is More preferably, it does not contain an inorganic filler of less than 0.1 μm. In addition, (C) an inorganic filler may be used individually by 1 type, and the thing of a different average particle diameter may be mixed and used for it.

  (C) A commercially available product may be used as the inorganic filler. Examples of commercially available (C) inorganic fillers include “SO-C1” (average particle diameter: 0.25 μm), “SO-C2” (average particle diameter: 0.5 μm), which are spherical silica, “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 manufactured by Admatechs Corporation) ) And the like.

  (C) The inorganic filler may be subjected to a surface treatment. For example, when silica is used as the inorganic filler (C), a silane coupling agent treatment may be applied as the surface treatment. Examples of the silane coupling agent include amino silane coupling agents, vinyl silane coupling agents, and epoxy silane coupling agents. Among these, silica subjected to surface treatment with an aminosilane coupling agent is preferable.

The amount of the (C) inorganic filler in the resin composition for adhesive films is defined as follows. First, the resin composition that forms a layer on the support film is dried at 200 ° C. for 30 minutes, the solvent contained in the resin composition is removed, and the weight (solid content) after the solvent is removed is measured. . The amount of (C) inorganic filler contained in the solid content is defined as the amount of (C) inorganic filler in the resin solid content.
In addition, as a method for measuring (C) the inorganic filler, if the amount of the solid content of the (C) inorganic filler to be blended is calculated in advance, the proportion in the solid content can be easily obtained. A calculation example in the case of using (C) inorganic filler dispersed in a solvent (hereinafter also referred to as “(C) inorganic filler dispersion”) is shown below.
The solid content of (C) inorganic filler in (C) inorganic filler dispersion was 70% by mass as a result of calculation after drying at 200 ° C. for 30 minutes. As a result of blending the resin composition using 40 g of this (C) inorganic filler dispersion liquid, the total amount of the obtained resin composition was 100 g. A result of drying 100 g of the resin composition at 200 ° C. for 30 minutes and measuring the weight of the solid content after drying was 60 g. Since the amount of the (C) inorganic filler contained in the solid content is 40 g × 70 mass% = 28 g, the amount of the (C) inorganic filler in the resin solid content is 28/60 = 47 mass%. (46.6% by mass).

  The amount of the (C) inorganic filler in the adhesive film resin composition is preferably as large as possible from the viewpoint of lowering the thermal expansion coefficient of the interlayer insulating layer after thermosetting. In view of embedding irregularities and through holes, there is an appropriate amount of inorganic filler. From such a viewpoint, the content of the (C) inorganic filler is 20 to 95% by mass in the resin solid content, preferably 30 to 90% by mass, and preferably 50 to 90% by mass. More preferred. (C) When the content of the inorganic filler is 20% by mass or more, the thermal expansion coefficient can be lowered, and when it is 95% by mass or less, the embedding property can be kept good.

<Flame Retardant>
The resin composition for adhesive films may further contain a flame retardant.
Although it does not specifically limit as a flame retardant, For example, an inorganic flame retardant, a resin flame retardant, etc. are mentioned.
Examples of the inorganic flame retardant include aluminum hydroxide and magnesium hydroxide exemplified as (C) inorganic filler.
The resin flame retardant may be a halogen-based resin or a non-halogen-based resin, but it is preferable to use a non-halogen-based resin in consideration of environmental burden. The resin flame retardant may be blended as a filler or may have a functional group that reacts with the thermosetting resin.
A commercially available product can be used as the resin flame retardant. Examples of commercially available resin flame retardants to be blended as fillers include “PX-200” (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.), which is an aromatic phosphate ester flame retardant, and a polyphosphate compound. “Exolit OP 930” (trade name, manufactured by Clariant Japan Co., Ltd.) and the like.
Examples of commercially available resin flame retardants having functional groups that react with thermosetting resins include epoxy phosphorus-containing flame retardants and phenol phosphorus-containing flame retardants. Examples of the epoxy-based phosphorus-containing flame retardant include “FX-305” (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). Examples of the phenol-based phosphorus-containing flame retardant include “HCA-HQ”. (Trade name) manufactured by Sanko Co., Ltd., “XZ92741” (trade name, manufactured by Dow Chemical Company), and the like. You may use these individually or in mixture of 2 or more types.

<(D) Solvent>
The adhesive film of the present invention contains (D) a solvent.
Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve, methyl carbitol, Examples thereof include carbitol compounds such as butyl carbitol; aromatic hydrocarbon compounds such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether. You may use these individually or in mixture of 2 or more types.
In the present specification, the solvent (D) contained in the adhesive film of the present invention may be referred to as “residual solvent”.

(Residual solvent amount)
The residual solvent amount in the adhesive film of the present invention is 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 2 to 10% by mass. When the amount of the residual solvent is 1% by mass or more, the handleability of the adhesive film is improved, and for example, occurrence of powder falling or cracking when cutting with a cutter can be suppressed. On the other hand, when it is 20% by mass or less, stickiness is suppressed and the film can be easily wound and unwound. Moreover, in order to enable unwinding, a protective film is often provided on the varnish-coated surface of the adhesive film after drying, but if the residual solvent amount is 20% by mass or less, the protective film and the adhesive film of the present invention Separation between them becomes easy.
Further, since the residual solvent is removed by drying and thermosetting in the process of producing the multilayer printed wiring board, it is preferable that the residual solvent is small from the viewpoint of environmental load, and the change in film thickness before and after drying and thermosetting is reduced. In order to achieve this, it is preferable that the amount is small.
In the production of the adhesive film of the present invention, it is preferable to determine the drying conditions so as to achieve a target residual solvent amount. Since the drying conditions vary depending on the type of solvent, the amount of the solvent, and the like contained in the resin composition, it is preferable to determine the drying conditions after performing the conditions in advance by each coating apparatus.

Here, the residual solvent amount in the present invention is the ratio (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. Thereafter, the support film and the resin composition layer formed thereon are left in a dryer at 200 ° C. for 10 minutes, and the weight after drying (W _c ) is measured. It can be calculated by the following formula using the obtained weights (W _a ) to (W _c ).
Ratio of solvent (% by mass) = (1-((W _c ) − (W _a )) / ((W _b ) − (W _a ))) × 100

<Other ingredients>
The adhesive film of this invention may contain the other component in the range which does not inhibit the effect of this invention. Examples of other components include thickeners such as olben and benton; UV absorbers such as thiazole and triazole; adhesion imparting agents such as silane coupling agents; phthalocyanine blue, phthalocyanine green, iodin green, and disazo yellow. And colorants such as carbon black; and optional resin components other than those described above.

[Support film]
The support film in the present invention is a support for producing the adhesive film of the present invention, and is usually finally peeled off or removed when producing a multilayer printed wiring board. .

Although it does not specifically limit as a support body film, For example, an organic resin film, metal foil, a release paper etc. are mentioned.
Examples of the material for the organic resin film include polyolefin such as polyethylene and polyvinyl chloride; polyester such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; polycarbonate and polyimide. Among these, PET is preferable from the viewpoints of price and handleability.
Examples of the metal foil include copper foil and aluminum foil. When copper foil is used for the support, the copper foil can be used as it is as a conductor layer to form a circuit. In this case, rolled copper, electrolytic copper foil, or the like can be used as the copper foil. Moreover, although the thickness of copper foil is not specifically limited, For example, what has a thickness of 2-36 micrometers can be used. When using thin copper foil, you may use copper foil with a carrier from a viewpoint of improving workability | operativity.
These support films and a protective film described later may be subjected to surface treatment such as mold release treatment, plasma treatment, corona treatment and the like. Examples of the release treatment include a release treatment with a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, and the like.
Although the thickness of a support body film is not specifically limited, From a viewpoint of handleability, it is preferable that it is 10-120 micrometers, It is more preferable that it is 15-80 micrometers, It is further more preferable that it is 15-70 micrometers.
The support film need not be a single component as described above, and may be formed of a plurality of layers (two or more layers) of different materials.

For example, when the support film has a two-layer structure, for example, as the first support film, the support film mentioned above is used, and as the second layer, an epoxy resin, an epoxy resin curing agent, The thing which has the layer formed from a filler etc. is mentioned. As the material used for the second layer, the materials listed in the materials used for the adhesive film of the present invention can also be used.
A layer formed on the first support film (may be a second layer or a plurality of layers of two or more layers) is a layer prepared with the intention of imparting a function, for example, It can be used for the purpose of improving adhesiveness with plated copper.
Although it does not restrict | limit especially as a formation method of a 2nd layer, For example, the method of apply | coating and drying the varnish which melt | dissolved and disperse | distributed each material in the solvent on the 1st layer support film is mentioned.

When the support film is formed of a plurality of layers, the thickness of the first support film is preferably 10 to 100 μm, more preferably 10 to 60 μm, and 13 to 50 μm. Further preferred.
The thickness of the layer formed on the first support film (the second and subsequent layers may be two or more layers) is preferably 1 to 20 μm. When it is 1 μm or more, the intended function can be achieved, and when it is 20 μm or less, the economical efficiency as a support film is excellent.

  When the support film is formed of a plurality of layers, when the support film is peeled off, the layer (which may be two or more layers) to be left on the multilayer printed wiring board side together with the adhesive film of the present invention is peeled off. Or you may isolate | separate into the layer (two or more layers may be removed) removed.

[Protective film]
The adhesive film of the present invention may have a protective film. The protective film is provided on the surface opposite to the surface on which the support for the adhesive film is provided, and is used for the purpose of preventing adhesion of foreign substances and the like to the adhesive film and scratches. The protective film is peeled off before the adhesive film of the present invention is laminated on a circuit board or the like by laminating or hot pressing.
Although it does not specifically limit as a protective film, The material similar to a support body film can be used. Although the thickness of a protective film is not specifically limited, For example, what has a thickness of 1-40 micrometers can be used.

[Production method of adhesive film]
The adhesive film of this invention can be manufactured by apply | coating and drying the resin composition for adhesive films on a support body film. The obtained adhesive film can be rolled up and stored and stored. More specifically, for example, after dissolving each resin component in the organic solvent, (C) an inorganic filler or the like is mixed to prepare a resin composition for an adhesive film, and the varnish is placed on a support film. It can be produced by coating, drying the organic solvent by heating, blowing hot air, or the like to form a resin composition layer on the support film.
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 in a semi-cured (B-stage) state. Good.

  The method for coating the varnish on the support film is not particularly limited. For example, the coating method may be performed using a known coating apparatus such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater. Can be applied. What is necessary is just to select a coating apparatus suitably according to the target film thickness.

[2] Second Invention Next, the resin composition, the resin film for an interlayer insulating layer, and the multilayer printed wiring board according to the second invention will be described.
Hereinafter, in the description of the second invention, when simply referred to as “resin composition”, it refers to the resin composition according to the second invention.

[Resin composition]
The resin composition of the present invention comprises (a) an epoxy resin (hereinafter also referred to as “component (a)”), (b) a cyanate resin (hereinafter also referred to as “component (b)”), and (c) active ester curing. Agent (hereinafter also referred to as “component (c)”), (d) a phosphorus-based curing accelerator (hereinafter also referred to as “component (d)”), and (e) an inorganic filler (hereinafter referred to as “component (e)”). It is also a resin composition containing.

<(A) Epoxy resin>
(A) Although it does not specifically limit as an epoxy resin, For example, the epoxy resin which has a 2 or more epoxy group in 1 molecule is mentioned preferably.
(A) As an epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, Bisphenol A novolac type epoxy resin, bisphenol S novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, anthracene novolac type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type Epoxy resins (including naphthol novolac type epoxy resins), fluorene type epoxy resins, xanthene type epoxy resins, anthraces Type epoxy resins. You may use these individually or in mixture of 2 or more types.
Among these, a cresol novolac type epoxy resin and a novolak type epoxy resin containing a naphthalene skeleton are preferable from the viewpoint of excellent reflow heat resistance of the obtained interlayer insulating layer. These may be used by mixing with a liquid epoxy resin such as bisphenol A type epoxy resin or bisphenol F type epoxy resin from the viewpoint of the handleability of the resulting resin film for an interlayer insulating layer.

  Moreover, from the viewpoint of obtaining excellent smear processability, a cresol novolac type epoxy resin and a phenol novolac type epoxy resin are preferable. Furthermore, from the viewpoint of achieving both heat resistance and smear removability, it is preferable to use an aralkyl novolac epoxy resin and an aralkyl novolac epoxy resin having a biphenyl skeleton in combination.

  (A) A commercially available product may be used as the epoxy resin. Commercially available (a) epoxy resins include “NC-3000-H”, “NC-3000-L”, “NC-3100”, “NC-3000” (Nippon Kayaku Co., Ltd., trade name) , Aralkyl novolak type epoxy resin having a biphenyl skeleton), “NC-7000-L” (manufactured by Nippon Kayaku Co., Ltd., trade name, naphthol novolak type epoxy resin), “Epicron (registered trademark) N673” (made by DIC Corporation) , Trade name, cresol novolac type epoxy resin), “Epiclon (registered trademark) 840S” (manufactured by DIC Corporation, trade name, liquid bisphenol A type epoxy resin) and the like.

(A) The epoxy equivalent of the epoxy resin is preferably 150 to 500 g / eq from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by plating. More preferably, it is 400 g / eq, and it is further more preferable that it is 200-300 g / eq.
Here, the epoxy equivalent is the mass of the resin per epoxy group (g / eq), and can be measured according to the method defined in JIS K 7236. Specifically, using an automatic titration device “GT-200 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., 2 g of epoxy resin was weighed into a 200 ml beaker, 90 ml of methyl ethyl ketone was dropped, dissolved in an ultrasonic cleaner, iced It is obtained by adding 10 ml of acetic acid and 1.5 g of cetyltrimethylammonium bromide and titrating with a 0.1 mol / L perchloric acid / acetic acid solution.

The content of the epoxy resin (a) in the resin composition of the present invention is 5 to 60 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition from the viewpoint of smear removability, dielectric loss tangent and heat resistance. It is preferable that it is 5-25 mass parts, It is more preferable that it is 7-20 mass parts, It is especially preferable that it is 8-18 mass parts.
Here, in this specification, “in terms of solid content” means that only non-volatile content excluding volatile components such as organic solvents is used as a reference. That is, 100 mass parts in terms of solid content means equivalent to 100 mass parts of nonvolatile content.

<(B) Cyanate resin>
(B) Although it does not specifically limit as cyanate resin, The cyanate resin which has a 2 or more cyanato group in 1 molecule is mentioned preferably.
(B) Examples of cyanate resin include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4-cyanatophenyl) methane, Bisphenol type cyanate resin such as 2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane; dicyclopentadiene type such as cyanate ester compound of phenol-added dicyclopentadiene polymer Cyanate resins; novolak-type cyanate resins such as phenol novolac-type cyanate ester compounds and cresol novolak-type cyanate ester compounds; α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene; prepolymers of these cyanate resins ( Hereinafter also referred to as “cyanate prepolymer”) Etc., and the like. You may use these individually or in mixture of 2 or more types.
Among these, the cyanate resin represented by the following general formula (III), the cyanate resin represented by the following general formula (IV), and the viewpoint of being easily available and having excellent dielectric properties and heat resistance of the obtained interlayer insulating layer; These prepolymers are preferred.

In the general formula (III), R ₇ is an alkylene group having 1 to 3 carbon atoms which may be substituted with a halogen atom, a sulfur atom, the following general formula (III-1) or the following general formula (III-2). The divalent group represented is shown. R ₈ and R ₉ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A plurality of R ₈ or R ₉ may be the same or different.

In General Formula (III-1), R ₁₀ represents an alkylene group having 1 to 3 carbon atoms. The plurality of R ₁₀ may be the same or different.

In the general formula (IV), R ₁₁ represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. n represents an integer of 1 or more. The plurality of R ₁₁ may be the same or different.
From the viewpoint of handleability, n is preferably 1-15, more preferably 1-10, and even more preferably 1-5.

In the general formula (III), the alkylene group having 1 to 3 carbon atoms represented by _{R 7,} a methylene group, an ethylene group, 1,2-propylene group, 1,3-propylene, 2,2-propylene Group (—C (CH ₃ ) ₂ —) and the like. Among these, a methylene group or a 2,2-propylene group (—C (CH ₃ ) ₂ —) is used from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by plating. Are preferred, and 2,2-propylene group (—C (CH ₃ ) ₂ —) is more preferred.
Examples of the halogen atom that substitutes for the alkylene group having 1 to 3 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the general formula (III-1), the alkylene group having 1 to 3 carbon atoms represented by R ₁₀ includes a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, 2,2 - propylene _{(-C (CH 3) 2 -} ) and the like.
Among these groups represented by R ₇ , from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by plating, a methylene group or a 2,2-propylene group (- C (CH ₃ ) ₂ —) is preferable, and a 2,2-propylene group (—C (CH ₃ ) ₂ —) is more preferable.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ₈ or R ₉ in the general formula (III) include a methyl group, an ethyl group, a propyl group, and a butyl group.

In the general formula (IV), examples of the alkyl group having 1 to 3 carbon atoms represented by R ₁₁ include a methyl group, an ethyl group, and a propyl group.
Examples of the halogen atom that substitutes the alkyl group having 1 to 3 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The cyanate prepolymer refers to (b) a polymer in which cyanate resins form a triazine ring by a cyclization reaction, and examples thereof include 3, 5, 7, 9, 11 mer of cyanate ester compounds. In this cyanate prepolymer, the conversion rate of the cyanate group is not particularly limited, but is preferably 30 to 90% by mass and preferably 35 to 85% by mass from the viewpoint of obtaining good solubility in an organic solvent. More preferably, it is more preferable that it is 40-80 mass%.
Examples of the cyanate prepolymer include a prepolymer of a cyanate resin represented by the general formula (III), a prepolymer of a cyanate resin represented by the general formula (IV), and the like. Among these, it is a prepolymer of a dicyanate compound having two cyanate groups in one molecule from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by plating. It is more preferable that it is a prepolymer of a cyanate resin represented by the general formula (III), and at least a part of 2,2-bis (4-cyanatophenyl) propane is triazine and trimerized. It is more preferable that it is a prepolymer (see the following formula (V)).

The weight average molecular weight (Mw) of the cyanate prepolymer is not particularly limited, but is preferably 500 to 100,000, more preferably 600 to 50,000 from the viewpoints of solubility in an organic solvent and workability, and 2000 to It is more preferable that it is 40000, and it is especially preferable that it is 3000-30000. If the weight average molecular weight (Mw) of the cyanate prepolymer is 500 or more, the crystallization of the cyanate prepolymer tends to be suppressed and the solubility in an organic solvent tends to be good. The increase is suppressed and the workability tends to be excellent.
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve. For details, the method described in Examples According to the measurement.

The cyanate prepolymer may be obtained by prepolymerizing the cyanate resin in the presence of a monofunctional phenol compound. When a cyanate prepolymer is produced, unreacted cyanato groups in the resulting cured product can be reduced by blending a monofunctional phenol compound, and thus moisture resistance and electrical characteristics tend to be excellent.
Examples of monofunctional phenolic compounds include alkyl group-substituted phenolic compounds such as p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol; p- (α-cumyl) phenol, mono-, Examples thereof include phenolic compounds represented by the following general formula (VI) such as di- or tri- (α-methylbenzyl) phenol. You may use these individually or in mixture of 2 or more types.

In general formula (VI), R ^a and R ^b each independently represent a hydrogen atom or a methyl group, and m represents an integer of 1 to 3. When m is an integer of 2 or 3, a plurality of R ^a or R ^b may be the same or different from each other.

  The compounding amount of the monofunctional phenol compound is the equivalent ratio between the phenolic hydroxyl group of the monofunctional phenol compound and the cyanate group contained in the (b) cyanate resin from the viewpoint of the dielectric properties and moisture resistance of the resulting interlayer insulating layer. (Hydroxyl group / cyanato group) is preferably in an amount of 0.01 to 0.30, more preferably in an amount of 0.01 to 0.20, and an amount of 0.01 to 0.15. More preferably. When the blending amount of the monofunctional phenol compound is within the above range, in addition to a tendency that a dielectric loss tangent is sufficiently low particularly in a high frequency band, good moisture resistance tends to be obtained.

There is no restriction | limiting in particular as a manufacturing method of cyanate prepolymer, A well-known manufacturing method is applicable.
A cyanate prepolymer can be suitably produced by, for example, reacting the dicyanate compound and the monofunctional phenol compound. By the reaction of the dicyanate compound and the monofunctional phenol compound, a compound having a group represented by —O—C (═NH) —O— (that is, imino carbonate) is formed, and the imino carbonate further reacts with each other. Alternatively, by reacting the imino carbonate and the dicyanate compound, a monofunctional phenol compound is eliminated while a cyanate prepolymer having a triazine ring is obtained. In the reaction, for example, the dicyanate compound and the monofunctional phenol compound are mixed and dissolved in the presence of a solvent such as toluene, and maintained at 80 to 120 ° C., and if necessary, such as zinc naphthenate. It can be carried out by adding a reaction accelerator.

(B) As cyanate resin, you may use a commercial item. Examples of commercially available (b) cyanate resins include bisphenol-type cyanate resins, novolac-type cyanate resins, and prepolymers in which some or all of these cyanate resins are triazines to form trimers.
Commercial products of bisphenol A type (2,2-bis (4-hydroxyphenyl) propane type) cyanate resin include “Primaset BADCy” (trade name, manufactured by Lonza), “Arocy B”. -10 "(trade name, manufactured by Huntsman) may be used. Commercially available products of bisphenol E type (1,1-bis (4-hydroxyphenyl) ethane type) cyanate resin include “Arocy L10” (trade name, manufactured by Huntsman), “Primaset”. ) LECy "(product name, manufactured by Lonza) or the like, and 2,2'-bis (4-cyanate-3,5-methylphenyl) ethane type cyanate resin commercially available (Primase) METHYLCy "(manufactured by Lonza) or the like may be used.
As a commercial product of the novolak-type cyanate resin, “Primaset PT30” (trade name, manufactured by Lonza), which is a phenol novolac-type cyanate resin, may be used.
Commercial products of cyanate resin prepolymers include “Primaset BA200” (trade name, made by Lonza) and “Primaset BA230S” (Lonza), which are prepolymers of bisphenol A type cyanate resin. Manufactured, trade name), etc., or “Primase BA3000” may be used.
In addition, “Arocy XU-371” (trade name, manufactured by Huntsman), “Arocy XP71787.02L” (trade name, manufactured by Huntsman), which is a cyanate resin containing a dicyclopentadiene structure, “Primaset DT-4000” (trade name, manufactured by Lonza), “Primaset DT-7000” (trade name, manufactured by Lonza) or the like may be used.

  The content of the (b) cyanate resin in the resin composition of the present invention is 2 to 50 with respect to 100 parts by mass in terms of solid content of the resin composition from the viewpoint of the dielectric loss tangent and heat resistance of the obtained interlayer insulating layer. It is preferable that it is a mass part, It is more preferable that it is 5-40 mass parts, It is further more preferable that it is 10-30 mass parts.

  In the resin composition of the present invention, the mass ratio [(a) / (b)] of (a) the epoxy resin and (b) the cyanate resin is from the viewpoint of the dielectric loss tangent and heat resistance of the resulting interlayer insulating layer. It is preferably 0.1 to 5, more preferably 0.3 to 2, and still more preferably 0.4 to 1.

<(C) Active ester curing agent>
(C) There is no restriction | limiting in particular if an active ester hardening | curing agent functions as a hardening | curing agent of an epoxy resin, and has an active ester.

  (C) As an active ester curing agent, it has a highly reactive ester group such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy ester compound, and curing action of epoxy resin. A compound or the like having can be used.

(C) The active ester curing agent is preferably a compound having two or more active ester groups in one molecule, and in one molecule obtained from a compound having a polyvalent carboxylic acid and an aromatic compound having a phenolic hydroxyl group. An aromatic compound having two or more active ester groups is more preferable, and is an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group. An aromatic compound having two or more ester groups in the molecule of the aromatic compound is more preferable. Further, (c) the active ester curing agent may contain a linear or multi-branched polymer.
If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with (a) the epoxy resin and (b) the cyanate resin can be increased. If it is a compound which has a group ring, heat resistance can be made high. In particular, from the viewpoint of heat resistance and the like, (c) the active ester curing agent is preferably an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.
Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. Among these, from the viewpoint of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are preferred, catechol, 1,5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzo More preferred are enone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetra Hydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are more preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are particularly preferable, dicyclopentadienyl diphenol, Phenol novolac is highly preferred and dicyclopentadienyl diphenol is most preferred.
Examples of the thiol compound include benzenedithiol and triazinedithiol.

(C) As the active ester curing agent, an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available product may be used.
Examples of commercially available (c) active ester curing agents include those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, benzoylated phenol novolacs, and among these, dicyclopentadienyl. Those containing a diphenol structure are preferred. Specifically, “EXB9451”, “EXB9460”, “EXB9460S-65T”, “HPC-8000-65T” (above, manufactured by DIC Corporation, trade name, activity) as those containing a dicyclopentadienyl diphenol structure. Group equivalent of about 223 g / eq), acetylated product of phenol novolak “DC808” (manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 149 g / eq), and benzoylated product of phenol novolac “YLH1026” (manufactured by Mitsubishi Chemical Corporation, active) Group equivalent of about 200 g / eq).

  (C) The active ester curing agent is not particularly limited and can be produced by a known method. Specifically, it can be obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.

  In the resin composition of the present invention, the content of the (c) active ester curing agent is 100 parts by mass in terms of solid content of the resin composition from the viewpoint of mechanical properties, curing time and dielectric properties of the obtained interlayer insulating layer. On the other hand, it is preferable that it is 2-30 mass parts, It is more preferable that it is 3-25 mass parts, It is further more preferable that it is 4-20 mass parts.

<(D) Phosphorous curing accelerator>
The resin composition of the present invention contains (d) a phosphorus-based curing accelerator from the viewpoint of enabling curing at a low temperature and in a short time. Moreover, the external appearance and smear removal property of the interlayer insulation layer obtained by hardening | curing with a support body become favorable by containing (d) phosphorus series hardening accelerator.

(D) Although it does not specifically limit as a phosphorus hardening accelerator, An organic phosphorus compound is preferable.
Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra Examples include phenylphosphonium tetraphenylborate, an addition reaction product of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound. Among these, an addition reaction product of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom is preferable, which is represented by the following general formula (I) as disclosed in JP2011-179008A. It is preferably an addition reaction product of a phosphine compound in which one or more alkyl groups are bonded to the phosphorus atom represented by the quinone compound represented by the following general formula (II).

In general formula (I), R ₁ represents an alkyl group having 1 to 12 carbon atoms, and R ₂ and R ₃ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In general formula (II), R _{4 to} R ₆ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ₄ and R ₅ may be bonded to each other to form a cyclic structure. Good.

The alkyl group having 1 to 12 carbon atoms represented by _{R 1} in formula (I), is not particularly limited, methyl, ethyl, propyl, isopropyl, n- butyl group, sec- butyl Group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and other chain alkyl groups; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups An aryl group-substituted alkyl group such as a benzyl group; an alkoxy group-substituted alkyl group such as a methoxy group-substituted alkyl group, an ethoxy group-substituted alkyl group, or a butoxy group-substituted alkyl group; an amino group-substituted alkyl group such as a dimethylamino group or a diethylamino group; Examples thereof include a hydroxyl group-substituted alkyl group.
Moreover, there is no restriction | limiting in particular as a C1-C12 hydrocarbon group represented by R < ₂ > and R < ₃ >, C1-C12 substituted or unsubstituted aliphatic hydrocarbon group, C1-C12 Substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups 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 R ₁ .
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, an alkyl group, an alkoxy group, an aryl group, and a hydroxyl group. , Amino groups, halogen-substituted and the like.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms include aryl groups such as phenyl group and naphthyl group; tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, Alkyl group-substituted aryl groups such as dimethylnaphthyl group; alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, methoxynaphthyl group; amino groups such as dimethylamino group and diethylamino group Substituted aryl groups; halogen-substituted aryl groups such as hydroxyphenyl groups and dihydroxyphenyl groups; aryloxy groups such as phenoxy groups and crezoxy groups; phenylthio groups, tolylthio groups, diphenylamino groups, and those substituted with amino groups, halogens, etc. Is mentioned. Of these, a substituted or unsubstituted alkyl group and aryl group are preferable.

  Examples of the phosphine compound represented by the general formula (I) include trialkylphosphine such as tricyclohexylphosphine, tributylphosphine, trioctylphosphine; cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, butyldiphenylphosphine, dibutylphenylphosphine, octyldiphenylphosphine. And alkyldiphenylphosphine such as dioctylphenylphosphine; from the viewpoint of varnish solubility, tributylphosphine, tri (p-methylphenyl) phosphine, tri (m-methylphenyl) phosphine, tri ( o-Methylphenyl) phosphine is particularly preferred.

The hydrocarbon group having 1 to 18 carbon atoms represented by R _{4 to} R ₆ in the general formula (II) is not particularly limited, and is a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms. A substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms, and the like.
Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl. Groups, octyl groups, decyl groups, dodecyl groups and other alkyl groups; allyl groups, methoxy groups, ethoxy groups, propoxyl groups, n-butoxy groups, tert-butoxy groups and other alkoxy groups; dimethylamino groups, diethylamino groups, etc. Alkylamino group; alkylthio group such as methylthio group, ethylthio group, butylthio group, dodecylthio group; substituted alkyl group such as amino group-substituted alkyl group, alkoxy-substituted alkyl group, hydroxyl group-substituted alkyl group, aryl group-substituted alkyl group; amino group substitution Substitution of alkoxy group, hydroxyl group-substituted alkoxy group, aryl group-substituted alkoxy group, etc. Such as alkoxy group, and the like.
Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and an alkyl group, an alkoxy group, an aryl group, and a hydroxyl group. , Amino groups, halogen-substituted and the like.
Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms include aryl groups such as phenyl group and tolyl group; alkyl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group and t-butylphenyl group Substituted aryl group; alkoxy group substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group; aryloxy group such as phenoxy group, crezoxy group; phenylthio group, tolylthio group, diphenylamino group, etc. And those substituted with an amino group, halogen or the like.
Among them, 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, a substituted or unsubstituted alkylthio group, and substituted or unsubstituted Of the arylthio group is preferred.

Further, the quinone compound represented by the general formula (II) may have a cyclic structure in which R ₄ and R ₅ are bonded. The polycyclic quinone compound in which R ₄ and R ₅ are bonded to form a cyclic structure is not particularly limited. ), And the like.

In general formulas (VII) to (IX), R ₆ is the same as in general formula (II).

  Among the quinone compounds represented by the general formula (II), 1,4-benzoquinone and methyl-1,4-benzoquinone are preferable from the viewpoint of reactivity with the phosphine compound, and from the viewpoint of curability during moisture absorption. Is an alkoxy group-substituted 1,4-benzoquinone such as 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, methoxy-1,4-benzoquinone; 1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, methyl-substituted 1,4-benzoquinone such as methyl-1,4-benzoquinone is preferred, and 2,5-diquinone is preferred from the viewpoint of storage stability. -T-Butyl-1,4-benzoquinone, t-butyl-1,4-benzoquinone, and phenyl-1,4-benzoquinone are preferred.

  Examples of the addition reaction product of the phosphine compound represented by the general formula (I) and the quinone compound represented by the general formula (II) include compounds represented by the following general formula (X).

In general formula (X), R _{1 to} R ₆ are the same as those in general formulas (I) and (II).

  Among addition reaction products of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom, from the viewpoint of curability during moisture absorption, an addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, Addition reaction product of cyclohexylphosphine and methyl-1,4-benzoquinone, Addition reaction product of tricyclohexylphosphine and 2,3-dimethyl-1,4-benzoquinone, Tricyclohexylphosphine and 2,5-dimethyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of tricyclohexylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tricyclohexylphosphine and 2,5-dimethoxy-1,4-benzoquino Addition reaction product of tributylphosphine and 1,4-benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, tributylphosphine and 2,3-dimethyl-1,4-benzoquinone , An addition reaction product of tributylphosphine and 2,5-dimethyl-1,4-benzoquinone, an addition reaction product of tributylphosphine and methoxy-1,4-benzoquinone, tributylphosphine and 2,3-dimethoxy -1,4-benzoquinone addition reaction product, tributylphosphine and 2,5-dimethoxy-1,4-benzoquinone addition reaction product, trioctylphosphine and 1,4-benzoquinone addition reaction product, trioctylphosphine Reaction product of trioctylphosphite with methyl-1,4-benzoquinone And 2,3-dimethyl-1,4-benzoquinone addition reaction product, trioctylphosphine and 2,5-dimethyl-1,4-benzoquinone addition reaction product, trioctylphosphine and methoxy-1,4-benzoquinone Of trioctylphosphine and 2,3-dimethoxy-1,4-benzoquinone, and addition reaction product of trioctylphosphine and 2,5-dimethoxy-1,4-benzoquinone. An addition reaction product of an alkyl phosphine and a quinone compound is preferable.

  From the viewpoint of reflow crack resistance, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2,3 -Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction of cyclohexyldiphenylphosphine and methoxy-1,4-benzoquinone Product, addition reaction product of cyclohexyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, butyldiphenylphosphine and , 4-benzoquinone addition reaction product, butyldiphenylphosphine and methyl-1,4-benzoquinone addition reaction product, butyldiphenylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction product, butyldiphenyl Addition reaction product of phosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and methoxy-1,4-benzoquinone, butyldiphenylphosphine and 2,3-dimethoxy-1,4- Addition reaction product of benzoquinone, addition reaction product of butyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, octyldiphenylphosphine and methyl-1 , 4-Benzoquinone addition reaction product, octyl diph Addition reaction product of nylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, octyldiphenylphosphine and methoxy-1,4 An addition reaction product of benzoquinone, an addition reaction product of octyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, an addition reaction product of octyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, Addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, addition of dicyclohexylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Reactant, dicyclohexylpheny Addition reaction product of ruphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methoxy-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,3-dimethoxy-1,4 An addition reaction product of benzoquinone, an addition reaction product of dicyclohexylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, an addition reaction product of dibutylphenylphosphine and methyl-1,4-benzoquinone, dibutylphenylphosphine and Addition reaction product of 2,3-dimethyl-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, dibutylphenylphosphine and methoxy-1,4-benzoquinone Addition reaction product, dibutylphenylphosphine And 2,3-dimethoxy-1,4-benzoquinone addition reaction product, dibutylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone addition reaction product, dioctylphenylphosphine and 1,4-benzoquinone Addition reaction product, dioctylphenylphosphine and methyl-1,4-benzoquinone addition reaction product, dioctylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone addition reaction product, dioctylphenylphosphine and 2,5 -Addition reaction product of dimethyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction of dioctylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone , Dioctylphenylphosphine and 2,5-dimethoxy- An addition reaction product of alkyldiphenylphosphine or dialkylphenylphosphine and a quinone compound, such as an addition reaction product of 1,4-benzoquinone, among them, an addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, butyldiphenylphosphine An addition reaction product of alkyldiphenylphosphine and 1,4-benzoquinone such as an addition reaction product of 1,4-benzoquinone and an addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone is more preferable.

  From the viewpoint of storage stability, addition reaction product of tricyclohexylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of tributylphosphine and t-butyl-1,4-benzoquinone, trioctylphosphine And t-butyl-1,4-benzoquinone addition reaction product, dicyclohexylphenylphosphine and t-butyl-1,4-benzoquinone addition reaction product, dibutylphenylphosphine and t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of dioctylphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone, butyldiphenylphosphine and t-butyl- Addition reaction product with 1,4-benzoquinone, octyldiphenyl Addition reaction product of sphin and t-butyl-1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, dibutyl-p-tolylphosphine and t-butyl- 1,4-benzoquinone addition reaction product, dioctyl-p-tolylphosphine and t-butyl-1,4-benzoquinone addition reaction product, cyclohexyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone An addition reaction product of butyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, an addition reaction product of octyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, Addition reaction product of tricyclohexylphosphine and phenyl-1,4-benzoquinone, tributylphosphine and phenyl Addition reaction product of 1,4-benzoquinone, addition reaction product of trioctylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and phenyl-1,4-benzoquinone, dibutylphenylphosphine and phenyl Addition reaction product of -1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and phenyl-1,4-benzoquinone, butyldiphenylphosphine and Addition reaction product of phenyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dicyclohexyl-p-tolylphosphine and phenyl-1,4-benzoquinone, Dibutyl Addition reaction product of p-tolylphosphine and phenyl-1,4-benzoquinone, Addition reaction product of dioctyl-p-tolylphosphine and phenyl-1,4-benzoquinone, cyclohexyldi-p-tolylphosphine and phenyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, addition reaction product of octyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, etc. Among these, an addition reaction product of tricyclohexylphosphine and t-butyl-1,4-benzoquinone, an addition reaction product of tributylphosphine and t-butyl-1,4-benzoquinone, trioctylphosphine and t-butyl- Addition reaction product with 1,4-benzoquinone, dicyclohexylphenylphosphite And t-butyl-1,4-benzoquinone addition reaction product, dibutylphenylphosphine and t-butyl-1,4-benzoquinone addition reaction product, dioctylphenylphosphine and t-butyl-1,4-benzoquinone Addition reaction product, addition reaction product of cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, octyldiphenylphosphine and t-butyl- An addition reaction product of a phosphine compound having at least one alkyl group and a quinone compound having a t-butyl group, such as an addition reaction product with 1,4-benzoquinone, is more preferable.

  Among the above, from the viewpoint of the reactivity between the phosphine compound and the quinone compound, an addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, an addition reaction product of tricyclohexylphosphine and methyl-1,4-benzoquinone, Addition reaction product of tributylphosphine and 1,4-benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, trioctylphosphine and methyl -1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and 1,4-benzoquinone addition reaction product, cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone addition reaction product, butyldiphenylphosphine and 1,4-benzoquinone With 4-benzoquinone Reaction product, addition reaction product of butyldiphenylphosphine and methyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, addition reaction of octyldiphenylphosphine and methyl-1,4-benzoquinone Phosphine compounds in which at least one alkyl group is bonded to a phosphorus atom, such as an addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, an addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, and the like. An addition reaction product with 1,4-benzoquinone or methyl-1,4-benzoquinone is more preferable.

There is no particular limitation on the method for producing an addition reaction product of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom. For example, a phosphine compound and a quinone compound used as raw materials are both dissolved. And an isolation method after an addition reaction in an organic solvent.
The addition reaction product of the phosphine compound and the quinone compound in which at least one alkyl group is bonded to the phosphorus atom may be used alone or in combination of two or more.

  The content of the (d) phosphorus curing accelerator in the resin composition of the present invention is preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition, The amount is more preferably 0.015 to 0.40 parts by mass, and further preferably 0.02 to 0.30 parts by mass. (D) When the content of the phosphorus-based curing accelerator is equal to or more than the lower limit value, a sufficient curing rate can be obtained, the flatness of the resin layer on the inner layer pattern, and the interlayer obtained by curing with a support. Excellent insulation layer appearance. Moreover, the handling and embedding property of the resin film for interlayer insulation layers obtained as the content of (d) phosphorus hardening accelerator below the said upper limit is excellent.

  In addition, a curing accelerator such as an organic metal salt, imidazole, and an amine curing accelerator may be used in combination with (d) a phosphorus curing accelerator as long as the effects of the present invention are not impaired.

<(E) Inorganic filler>
The resin composition of the present invention further contains (e) an inorganic filler.
(E) As inorganic fillers, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate Strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica is preferable because it is inexpensive. You may use these individually or in mixture of 2 or more types.

(E) The inorganic filler is not particularly limited, but may be spherical from the viewpoint of fluidity (pattern embedding property) at the time of laminating a resin film for an interlayer insulating layer produced using the resin composition of the present invention. preferable.
(E) The volume average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.05 to 3 μm from the viewpoint of good circuit board embedding and insulation reliability between layers and wirings. More preferably, it is 2-3 micrometers, and it is further more preferable that it is 0.3-2.5 micrometers. In addition, the (e) inorganic filler used may have one type of volume average particle diameter, or may be used by mixing different volume average particle diameters.
The volume average particle diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and the particle diameter using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like.

  (E) Commercially available products may be used as the silica used as the inorganic filler. As commercially available silica, “SO-C1” (average particle size: 0.25 μm, product name), “SO-C2” (average particle size: 0.5 μm, product name) manufactured by Admatechs Co., Ltd., “ “SO-C3” (average particle size: 0.9 μm, product name), “SO-C5” (average particle size: 1.6 μm, product name), “SO-C6” (average particle size: 2.2 μm, product) Name).

(E) From the viewpoint of improving moisture resistance, an inorganic filler surface-treated with a surface treatment agent such as a silane coupling agent may be used as the inorganic filler.
Examples of the silane coupling agent include amino silane coupling agents, vinyl silane coupling agents, and epoxy silane coupling agents.
Among these, from the viewpoint of storage stability of the resin film for an interlayer insulating layer to which the resin composition of the present invention is applied, a spherical shape subjected to at least one surface treatment selected from a vinyl silane coupling agent and an epoxy silane coupling agent. It is preferred to use silica. When the compounding ratio of the epoxy silane coupling agent is increased, the heat resistance tends to be improved.
The silica which performed these surface treatments may use a single item, and may use together the silica which performed the different silane coupling agent process.
These silicas may be used in the form of a silica slurry previously dispersed in a solvent.

  The content of the inorganic filler (e) in the resin composition of the present invention is based on 100 parts by mass in terms of solid content of the resin composition from the viewpoint of low thermal expansion, high frequency characteristics, and embedding in a wiring pattern. It is preferably 40 to 85 parts by mass, more preferably 50 to 85 parts by mass, and even more preferably 55 to 80 parts by mass. (E) When the content of the inorganic filler is 40 parts by mass or more, good low thermal expansibility and high-frequency characteristics tend to be obtained, and when it is 85 parts by mass or less, good embedding in a wiring pattern. Tends to be obtained.

<(F) Dicyandiamide>
The resin composition of the present invention preferably contains (f) dicyandiamide (hereinafter also referred to as “component (f)”). (F) Dicyandiamide is a curing agent for (a) epoxy resin. (F) By containing dicyandiamide, the adhesive strength between the inner layer circuit pattern and the interlayer insulating layer tends to be excellent.
(F) From the viewpoint of ease of blending, dicyandiamide is preferably blended after being dissolved or dispersed in an organic solvent in advance. (F) The organic solvent for dissolving or dispersing dicyandiamide is preferably methylene glycol monomethyl ether, propylene glycol monomethyl ether, dimethylacetamide, or N-methyl-2-pyrrolidone, and more preferably propylene glycol monomethyl ether from the viewpoint of safety. .
When the resin composition of the present invention contains (f) dicyandiamide, the content of (f) dicyandiamide is 0.01 to 0.1 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition. It is preferable. (F) If the dicyandiamide content is 0.01 parts by mass or more, the adhesive strength between the inner layer circuit pattern and the interlayer insulating layer of the present invention tends to be excellent, and if it is 0.1 parts by mass or less, (f ) Precipitation of dicyandiamide can be suppressed.

<(G) Phenoxy resin>
The resin composition of the present invention preferably contains (g) a phenoxy resin (hereinafter also referred to as “component (g)”). (G) By containing a phenoxy resin, the adhesive strength between the obtained interlayer insulating layer and the conductor layer tends to be improved, and the roughened shape of the surface of the interlayer insulating layer tends to be small and dense. . Moreover, when forming a conductor layer on an interlayer insulation layer using an electroless plating method, generation | occurrence | production of a plating blister is suppressed and it exists in the tendency for the adhesive strength of an interlayer insulation layer and a soldering resist to improve.
(G) The weight average molecular weight of the phenoxy resin is preferably 5,000 to 100,000 from the viewpoint of improving the solubility in an organic solvent and the mechanical strength and chemical resistance of the interlayer insulating layer. (G) By making the weight average molecular weight of a phenoxy resin into the said range, it exists in the tendency for generation | occurrence | production of the blister of a conductor layer to be suppressed.

  (G) As the phenoxy resin, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol AF skeleton, bisphenol trimethylcyclohexane skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, Those having one or more kinds of skeletons selected from naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, trimethylcyclohexane skeleton, and copolymer skeleton of styrene and glycidyl methacrylate can be used. Among these, from the viewpoint of improving the chemical resistance of the interlayer insulating layer and from the viewpoint of easily imparting appropriate irregularities to the interlayer insulating layer with an oxidizing agent in roughening, desmear treatment, etc., a phenoxy having a biphenyl skeleton Resins are preferred. You may use these individually or in mixture of 2 or more types. (G) The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

  (G) A commercially available product may be used as the phenoxy resin. Commercially available (g) phenoxy resins include bisphenol AF skeleton-containing phenoxy resins “YL7383” and “YL7384” (both trade names manufactured by Mitsubishi Chemical Corporation), bisphenol A skeleton-containing phenoxy resin “1256”, "4250" (both manufactured by Mitsubishi Chemical Co., Ltd., trade name), "YP-50" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), "YX8100" (Mitsubishi Chemical Corporation) which is a phenoxy resin containing a bisphenol S skeleton Product name), “YX6954” (trade name, manufactured by Mitsubishi Chemical Co., Ltd.), a phenoxy resin containing bisphenolacetophenone skeleton, “FX-293” (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Product name), phenoxy resin containing bisphenoltrimethylcyclohexane skeleton "YL7213" (trade name, manufactured by Mitsubishi Chemical Corporation), "FX-280" (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), "YL7553", "YL6794", "YL7290", "YL7482" ( As mentioned above, Mitsubishi Chemical Co., Ltd., a brand name) etc. can be used.

  (G) Although there is no restriction | limiting in particular in the manufacturing method of a phenoxy resin, For example, according to the manufacturing method of a well-known phenoxy resin from the bisphenol compound containing a trimethylcyclohexane structure or the bisphenol compound containing a terpene structure, and a bifunctional epoxy resin as a raw material Thus, it can be easily produced by reacting the epoxy group and the phenolic hydroxyl group in an equivalent ratio of about 1: 0.9 to 1: 1.1.

  When the resin composition of the present invention contains (g) phenoxy resin, the content of (g) phenoxy resin is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition. 1-10 mass parts is more preferable. (G) When the content of the phenoxy resin is 1 part by mass or more, sufficient flexibility is obtained, the handleability is excellent, and the peel strength of the conductor layer formed by plating tends to be excellent. When the content is less than or equal to part, sufficient fluidity is obtained during lamination, and an appropriate roughness tends to be obtained.

<(H) Resin having a siloxane skeleton>
The resin composition of the present invention preferably contains (h) a resin having a siloxane skeleton (hereinafter also referred to as “(h) siloxane resin”).
(H) The siloxane resin is not particularly limited, but is preferably a resin having a polysiloxane skeleton. When the resin composition of the present invention contains (h) a siloxane resin, when the resin composition of the present invention is varnished to produce a resin film for an interlayer insulating layer, repellency, undulation, etc. It becomes easy to apply uniformly without generating.
(H) Examples of the siloxane resin include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and polyether-modified polymethylalkylsiloxane. Etc.
(H) A commercially available product can be used as the siloxane resin. Examples of commercially available (h) siloxane resins include “BYK-310”, “BYK-313”, “BYK-300”, “BYK-320”, “BYK-330” and the like manufactured by Big Chemie Japan. It is done. You may use these individually or in mixture of 2 or more types.

  When the resin composition of this invention contains (h) siloxane resin, content of (h) siloxane resin is 0.005-1 mass part with respect to 100 mass parts of solid content conversion of a resin composition. It is preferably 0.01 to 0.8 parts by mass, and more preferably 0.02 to 0.5 parts by mass. (H) When the content of the siloxane resin is 0.005 parts by mass or more, the occurrence of waviness and the like during the coating is suppressed and uniform application is facilitated, and when it is 1 part by mass or less, the roughened shape after desmearing Becomes homogeneous and heat resistance is also good.

<Other ingredients>
The resin composition of the present invention may contain components other than the above components as long as the effects of the present invention are not impaired. Examples of other components include resin components other than the above components (hereinafter also referred to as “other resin components”), additives, organic solvents, and the like.

(Other resin components)
Examples of other resin components include thermosetting resins and thermoplastic resins other than the above components.
Although it does not specifically limit as a thermosetting resin which is another resin component, What is thermosetting at 150-200 degreeC is preferable. This temperature corresponds to a thermosetting temperature normally used when forming an interlayer insulating layer of a multilayer printed wiring board. Examples of such thermosetting resins include polymers of bismaleimide compounds and diamine compounds, bismaleimide compounds, bisallyl nazide resins, benzoxazine compounds, and the like. Among these, a polymer of a bismaleimide compound and a diamine compound is preferable.

(Additive)
Additives include thickeners such as olben and benton; adhesion imparting agents such as imidazole, thiazole, triazole and silane coupling agents; flame retardants; rubber particles; phthalocyanine blue, phthalocyanine green, iodin green, disazo Examples thereof include colorants such as yellow and carbon black.

(Flame retardants)
The resin composition of the present invention may contain a flame retardant. Examples of the flame retardant include an inorganic flame retardant and a resin flame retardant.
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, but a non-halogen-based resin is preferable in consideration of environmental load.

(Organic solvent)
The resin composition of the present invention may be made into a varnish state by containing an organic solvent from the viewpoint of facilitating handling and forming a resin film for an interlayer insulating layer described later.
Although it does not specifically limit as an organic solvent, Ketone type solvents, such as acetone, methyl ethyl ketone (henceforth "MEK"), methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carb Acetate solvents such as tol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Can be mentioned. You may use these individually or in mixture of 2 or more types. Among these, from the viewpoint of solubility, a ketone solvent is preferable, and MEK and methyl isobutyl ketone are more preferable.

  The resin composition of the present invention can be produced by mixing the components (a) to (e) and, if necessary, other components. As a mixing method, a known method can be applied, and mixing can be performed using a bead mill or the like.

[Resin film for interlayer insulation layer]
The resin film for interlayer insulation layers of the present invention (hereinafter also simply referred to as “resin film”) is a resin film for interlayer insulation layers having a support, an adhesion auxiliary layer, and a resin composition layer for interlayer insulation layers in this order. The resin composition layer for an interlayer insulating layer contains the resin composition of the present invention. The resin film of the present invention is used for a build-up multilayer printed wiring board, and can form a conductor layer having high adhesive strength on a smooth interlayer insulating layer. In the present invention, “smooth” means that the surface roughness Ra is less than 0.3 μm.
Note that there is no clear interface between the adhesion auxiliary layer and the resin composition layer for interlayer insulation layers. For example, some of the components of the adhesion auxiliary layer are contained in the resin composition layer for interlayer insulation layers. It may be in a fluidized state.

<Resin composition layer for interlayer insulation layer>
The resin composition layer for an interlayer insulating layer contains the resin composition of the present invention. When a multilayer printed wiring board is produced using the resin film of the present invention, the resin composition layer is in direct contact with the circuit board during lamination. It is a layer that melts and flows into the wiring pattern to embed the circuit board. Further, when there are through holes, via holes, and the like on the circuit board, they flow into them to fill the holes.
The resin composition layer for interlayer insulation layers can be obtained by layering the resin composition of the present invention. Layer formation can be performed by, for example, applying and drying the resin composition of the present invention after dissolving and / or dispersing in the organic solvent to form a varnish.

  Although the thickness of the resin composition layer for interlayer insulation layers can be determined by the thickness of the conductor layer formed on the printed wiring board, the thickness of the conductor layer is usually 5 to 70 μm. 100 μm is preferable, and from the viewpoint of enabling the multilayer printed wiring board to be thinned, it is more preferably 15 to 80 μm, and more preferably 20 to 50 μm while having a thickness equal to or greater than the conductor layer. Further preferred.

<Adhesion auxiliary layer>
The adhesion auxiliary layer is a layer that insulates the multilayered circuit patterns from each other in the multilayer printed wiring board that is multilayered by the build-up method, and that plays a role of smooth and high plating peel strength.
The thickness of the adhesion auxiliary layer is preferably 1 to 15 μm from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and high adhesion to a conductor layer formed by plating. Is more preferable, and it is still more preferable that it is 1-7 micrometers.
The adhesion auxiliary layer can be obtained by forming a layer of the resin composition for the adhesion auxiliary layer.

(Resin composition for adhesion auxiliary layer)
The resin composition for the adhesion auxiliary layer is not particularly limited, but preferably contains a thermosetting resin.
Examples of the thermosetting resin include an epoxy resin having two or more epoxy groups in one molecule, a polymer of a bismaleimide compound and a diamine compound, a cyanate ester compound, a bismaleimide compound, a bisallyl azide resin, and a benzoxazine compound. Among these, from the viewpoint of storage stability of the resin film for an interlayer insulating layer, (i) epoxy resin (hereinafter also referred to as “(i) component”), (j) cyanate resin (hereinafter referred to as “(j) component”). Bismaleimide compounds are also preferred, and it is more preferred to contain (i) an epoxy resin and (j) a cyanate resin.

<(I) Epoxy resin>
(I) Although it does not specifically limit as an epoxy resin, The thing similar to the (a) epoxy resin which the resin composition of this invention can contain is mentioned. Among these, from the viewpoint of excellent reflow heat resistance of the obtained interlayer insulating layer, an aralkyl novolak type epoxy resin is preferable, and an aralkyl novolak type epoxy resin having a biphenyl skeleton is more preferable.
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 the molecule, and includes an epoxy resin containing a structural unit represented by the following general formula (XI) Is mentioned.

In general formula (XI), R ₁₂ represents a hydrogen atom or a methyl group.

The content of the structural unit represented by the general formula (XI) in the epoxy resin containing the structural unit represented by the general formula (XI) has a small surface roughness after desmearing, and is a conductor layer formed by plating. From the viewpoint of obtaining an interlayer insulating layer having excellent adhesive strength, it is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and further preferably 80 to 100% by mass.
From the same viewpoint, the epoxy resin containing the structural unit represented by the general formula (XI) is preferably an epoxy resin represented by the following general formula (XII).

In general formula (XII), R ₁₃ represents a hydrogen atom or a methyl group, and s represents an integer of 1 or more. The plurality of R ₁₃ may be the same or different.
From the viewpoint of reducing the surface roughness after desmearing, s is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 8.

  The content of the (i) epoxy resin in the resin composition for the adhesion auxiliary layer is that of the resin composition for the adhesion auxiliary layer from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and high adhesion to the conductor layer. The amount is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 40 to 60 parts by mass with respect to 100 parts by mass in terms of solid content.

<(J) Cyanate resin>
(J) Although it does not specifically limit as cyanate resin, The thing similar to (b) cyanate resin which the resin composition of this invention can contain is mentioned.
The content of the (j) cyanate resin in the resin composition for an adhesion auxiliary layer is that the resin composition for the adhesion auxiliary layer has a smooth surface and is obtained from the viewpoint of obtaining an interlayer insulating layer having high adhesion to the conductor layer. The amount is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 20 to 35 parts by mass with respect to 100 parts by mass in terms of solid content.

<(K) Inorganic filler having a specific surface area of 20 m ² / g or more>
The resin composition for an adhesion auxiliary layer contains (k) an inorganic filler having a specific surface area of 20 m ² / g or more (hereinafter also simply referred to as “(k) inorganic filler” or “(k) component”). Is preferred.
(K) The inorganic filler makes it possible to prevent the resin from scattering and to adjust the shape of the laser processing when laser processing the interlayer insulating layer formed by thermosetting the resin composition of the present invention. Important from the point of view. In addition, when the surface of the interlayer insulating layer is roughened with an oxidizing agent, it is possible to form an appropriate roughened surface and to form a conductor layer having excellent adhesive strength by plating.

(K) As inorganic filler, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate Strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. Among these, silica is preferable because it is inexpensive. You may use these individually or in mixture of 2 or more types.
In addition, (k) the inorganic filler is preferably an inorganic filler that is surface-treated with a surface treatment agent such as a silane coupling agent in order to improve moisture resistance.

(K) The inorganic filler preferably has a small particle diameter from the viewpoint of forming fine wiring. From the same viewpoint, (k) the inorganic filler is a specific surface area of ^{20 m} 2 / g or more, preferably 60~200m ² / g, more preferably 90~130m ² / g .
The specific surface area can be determined by a BET method by low-temperature low-humidity physical adsorption of an inert gas. Specifically, molecules having a known adsorption occupation area such as nitrogen are adsorbed on the surface of the powder particles at the liquid nitrogen temperature, and the specific surface area of the powder particles can be determined from the amount of adsorption.
(K) The shape of the inorganic filler is not particularly limited, and can be an arbitrary shape. Therefore, it is preferable to adjust the specific surface area to the above range from the viewpoint of expressing the effects such as the formation of the appropriate roughened surface and the formation of the conductor layer having excellent adhesive strength, and particularly, fumed silica, colloidal, which will be described later. Since silica or the like is not spherical, it is important to define the specific surface area.

(K) As an inorganic filler, a commercial item may be used, and “AEROSIL (Aerosil) (registered trademark) R972” which is fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name, specific surface area 110 ± 20 m ² / g) and “AEROSIL (registered trademark) R202” (manufactured by Nippon Aerosil Co., Ltd., trade name, specific surface area 100 ± 20 m ² / g), “PL-1” which is colloidal silica (manufactured by Fuso Chemical Industries, Ltd.) , Trade name, specific surface area 181 m ² / g) and “PL-7” (manufactured by Fuso Chemical Industries, trade name, specific surface area 36 m ² / g). Among these, from the viewpoint of insulation reliability and heat resistance, (i) those having good dispersibility in the epoxy resin are preferable, and “AEROSIL (Aerosil) (manufactured by Nippon Aerosil Co., Ltd.) whose surface has been subjected to a hydrophobic treatment. “Registered trademark” R972 ”(trade name),“ AEROSIL (registered trademark) R202 ”manufactured by the same company, and the like are preferable.

  The content of the (k) inorganic filler in the resin composition for the adhesion auxiliary layer is preferably 3 to 40 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition for the adhesion auxiliary layer. More preferably, it is -30 mass parts, More preferably, it is 7-20 mass parts. (K) When the content of the inorganic filler is 3 parts by mass or more, resin scattering can be prevented during laser processing, and the laser processing shape of the interlayer insulating layer can be adjusted, and when it is 40 parts by mass or less, High plating peel strength can be obtained.

<(M) Polyamide resin containing polybutadiene skeleton>
The resin composition for an auxiliary adhesion layer preferably contains (m) a polyamide resin containing a polybutadiene skeleton (hereinafter also referred to as “(m) polyamide resin” or “(m) component”). In the present invention, the “polyamide resin” means a polymer having an amide bond (—NHCO—) in the main chain, and may be a polyamideimide resin having an amide bond and an imide bond. A polyamide resin having no imide bond is preferable.

  (M) The polyamide resin includes a structural unit represented by the following general formula (XIII), a structural unit represented by the following general formula (XIV), and a structural unit represented by the following general formula (XV) (Hereinafter also referred to as “modified polyamide resin”) is preferable.

In the general formulas (XIII) to (XV), a, b, c, x, y and z are average polymerization degrees, a is 2 to 10, b is 0 to 3, and c is 3 to 30. An integer, y + z = 2 to 300 ((y + z) / x) for x = 1, and z ≧ 20 (z / y) for y = 1.
R, R ′ and R ″ are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and R ′ ″ is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or both ends. It is a divalent group derived from an oligomer having a carboxy group.

Examples of the aromatic diamine used in the production of the modified polyamide resin include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, and diaminodiphenyl ether. , Diaminodimethyldiphenyl ether, methylenediamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis (diethoxyaniline) Isopropylidenedianiline, diaminobenzophenone, diamino Methylbenzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.
Aliphatic diamines used in the production of the modified polyamide resin include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, cyclohexanediamine, and azapentanediamine. , Triazaundecadiamine and the like. You may use these individually or in mixture of 2 or more types.

Examples of the phenolic hydroxyl group-containing dicarboxylic acid used for producing the modified polyamide resin include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid.
Examples of the dicarboxylic acid containing no phenolic hydroxyl group used in the modified polyamide resin include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having carboxy groups at both ends.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, biphenyl dicarboxylic acid, methylene dibenzoic acid, thiodibenzoic acid, carbonyl dibenzoic acid, sulfonylbenzoic acid, and naphthalenedicarboxylic acid.
Aliphatic dicarboxylic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di (meth) acryloyl Examples include oxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, (meth) acrylamide malic acid, and the like. You may use these individually or in mixture of 2 or more types.

(M) A commercially available product may be used as the polyamide resin. Examples of commercially available (m) polyamide resins include polyamide resins “BPAM-01” and “BPAM-155” (both trade names) manufactured by Nippon Kayaku Co., Ltd.
(M) As the polyamide resin, “BPAM-01” and “BPAM-155” are preferable from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by plating. Since “BPAM-155” is a rubber-modified polyamide having an amino group at the terminal and has reactivity with an epoxy group, (m) an interlayer obtained from a resin composition containing “BPAM-155” as a polyamide resin The insulating layer is more excellent in adhesive strength with a conductor layer formed by plating, and the surface roughness tends to be reduced.

(M) The number average molecular weight of the polyamide resin is preferably 20000 to 30000, more preferably 22000 to 29000, from the viewpoints of solubility in a solvent and film thickness retention of the adhesion auxiliary layer after lamination. Preferably, it is 24000-28000, and more preferably.
(M) 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 further preferably 105,000 to 120,000.
The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve, and details are described in Examples. It was measured according to the method.

  The content of the (m) polyamide resin in the adhesion auxiliary layer resin composition is preferably 3 to 13 parts by mass with respect to 100 parts by mass in terms of solid content of the adhesion auxiliary layer resin composition. It is more preferably 10 to 10 parts by mass, and further preferably 4 to 12 parts by mass. (M) When the content of the polyamide resin is 3 parts by mass or more, the adhesive strength with a conductor layer formed by a plating method tends to be excellent, and when it is 13 parts by mass or less, the interlayer insulating layer is roughened by an oxidizing agent. When the treatment is performed, the surface roughness of the interlayer insulating layer tends to be suppressed, and the reflow heat resistance tends to be excellent.

<(N) Phenoxy resin>
The resin composition for an auxiliary adhesion layer preferably contains (n) a phenoxy resin (hereinafter also referred to as “(n) component”).
(N) Although it does not specifically limit as a phenoxy resin, The thing similar to the (g) phenoxy resin which the resin composition of this invention can contain is mentioned.
The content of (n) phenoxy resin in the resin composition for the adhesion auxiliary layer has a smooth surface, a viewpoint of obtaining an interlayer insulating layer having high adhesion to a conductor layer formed by a plating method, and a plating blister From the viewpoint of suppressing the generation of the above, it is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition for the adhesion auxiliary layer. More preferably, it is -12 mass parts.

  The resin composition for an adhesion auxiliary layer may contain components other than the above components as long as the effects of the present invention are not impaired. Examples of the other components include the same components as the other components that may be contained in the resin composition of the present invention.

From the viewpoint of facilitating handling, the resin composition for the adhesion auxiliary layer may contain an organic solvent to be in a varnish state. Each component constituting the resin composition for the adhesion auxiliary layer is dissolved or dissolved in the organic solvent. It is preferable that it is uniformly dispersed.
Although it does not specifically limit as an organic solvent, In this invention, if it is a liquid at normal temperature of 20-30 degreeC and has a property which melt | dissolves resin, it can be used. Moreover, it is necessary to be an organic solvent which does not react with a thermosetting resin etc., and the cresol etc. which have a phenolic hydroxyl group are excluded.
Organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate; cellosolve, methyl carbitol, butyl Examples thereof include carbitols such as carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, and the like. You may use these individually or in mixture of 2 or more types.

<Support>
Although it does not specifically limit as a support body used for the resin film of this invention, An organic resin film, metal foil, release paper, etc. are mentioned.
Examples of the material for the organic resin film include polyolefin such as polyethylene and polyvinyl chloride; polyester such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; polycarbonate and polyimide. Among these, PET is preferable from the viewpoints of price and handleability.
Examples of the metal foil include copper foil and aluminum foil. When copper foil is used for the support, the copper foil can be used as it is as a conductor layer to form a circuit.
In this case, rolled copper, electrolytic copper foil, or the like can be used as the copper foil. Moreover, although the thickness of copper foil is not specifically limited, For example, what has a thickness of 2-36 micrometers can be used. When using thin copper foil, you may use copper foil with a carrier from a viewpoint of improving workability | operativity.

The support may be subjected to release treatment in addition to mat treatment and corona treatment.
The thickness of a support body is 10-150 micrometers normally, Preferably it is 25-50 micrometers. By making the thickness of the support 10 μm or more, the handleability becomes easy. On the other hand, since the support is usually finally peeled or removed, the thickness is preferably 150 μm or less from the viewpoint of energy saving or the like.

<Protective film>
The resin film of the present invention may have a protective film. The protective film is provided on the surface opposite to the surface on which the resin film support of the present invention is provided, and is used for the purpose of preventing adhesion and scratches of foreign matters to the resin film. . The protective film is peeled off before laminating the resin film of the present invention on a circuit board or the like by laminating or hot pressing.
Although it does not specifically limit as a protective film, The material similar to a support body can be used. Although the thickness of a protective film is not specifically limited, For example, what has a thickness of 1-40 micrometers can be used.

<Method for producing resin film>
As a method for producing the resin film of the present invention, for example, after coating a resin composition for an adhesion auxiliary layer in a varnish state on a support, it is dried by heating, hot air spraying, etc., and adhered onto the support A method of forming a resin composition layer for an interlayer insulating layer after forming an auxiliary layer, coating the varnish of the resin composition of the present invention in a varnish state on the adhesion auxiliary layer, and then drying. Etc.
As another method, for example, an adhesion auxiliary layer is formed on a support by the above-described method, and a resin composition layer for an interlayer insulating layer is separately formed on a peelable film and formed on the support. The adhesion auxiliary layer and the resin composition layer for an interlayer insulating layer formed on the film are arranged such that the surface on which the adhesion auxiliary layer is formed and the surface on which the resin composition layer for the interlayer insulation layer is formed are in contact with each other. The method of laminating etc. is also mentioned. In this case, the film which can peel the resin composition layer for interlayer insulation layers can also play a role as a protective film of a resin film.

  A method for coating the resin composition of the present invention and the resin composition for the adhesion auxiliary layer is not particularly limited, but known coating apparatuses such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater. The method of coating using can be applied. What is necessary is just to select a coating apparatus suitably according to the target film thickness.

Although it does not specifically limit as drying conditions after coating the resin composition of this invention, and the resin composition for adhesion auxiliary layers, It is so that content of the organic solvent in the resin film obtained may be 10 mass% or less. It is preferable to dry so that it may become 5 mass% or less. Since the drying conditions also affect the temperature-melt viscosity curve of the resin composition of the present invention, it is preferable to set the drying conditions so as to satisfy the handleability of the film.
The drying conditions vary depending on the amount and type of the organic solvent in the varnish. For example, if the varnish contains 30 to 80% by mass of the organic solvent, by drying at 50 to 150 ° C. for about 3 to 10 minutes A resin film can be formed.
It is preferable to set suitable drying conditions as appropriate by simple experiments.
Moreover, a resin film can be wound up in roll shape and preserve | saved and stored.

[Multilayer printed wiring board]
The multilayer printed wiring board of this invention contains the hardened | cured material of the resin composition of this invention, or the resin film for interlayer insulation layers.
The multilayer printed wiring board of the present invention can be produced, for example, by laminating the resin film of the present invention on a circuit board. Specifically, the following steps (1) to (6) [however, step (3) is arbitrary. ], And the support may be peeled off or removed after step (1), (2) or (3).

(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 laminating step (1)].
(2) A step of thermosetting the laminated resin film to form an insulating layer [hereinafter referred to as an insulating layer forming step (2)].
(3) A step of drilling a circuit board on which an insulating layer is formed [hereinafter referred to as a drilling 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 conductor layer by plating on the surface of the roughened insulating layer [hereinafter referred to as a conductor layer forming step (5)].
(6) A step of forming a circuit on the 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 the circuit board using a vacuum laminator. A commercially available vacuum laminator can be used as the vacuum laminator. Commercially available vacuum laminators include vacuum applicators manufactured by Nichigo-Morton Co., Ltd., vacuum press laminators manufactured by Meiki Seisakusho Co., Ltd., roll-type dry coaters manufactured by Hitachi, Ltd., and vacuums manufactured by Hitachi Chemical Electronics Co., Ltd. Laminator etc. are mentioned.

When a protective film is provided on the resin film, after peeling or removing the protective film, the circuit is applied while applying pressure and heating so that the resin composition layer for the interlayer insulating layer of the resin film is in contact with the circuit board. Lamination can be achieved by pressure bonding to the substrate.
In the lamination, for example, a resin film and a circuit board are preheated (preheated) as necessary, and then a pressure bonding temperature (laminating temperature) is 60 to 140 ° C. and a pressure bonding pressure is 0.1 to 1.1 MPa (9. 8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ) and an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.

In the insulating layer forming step (2), first, the resin film laminated on the circuit board in the laminating step (1) is cooled to around room temperature.
In the case of peeling the support, after peeling, the resin film laminated on the circuit board is heated and cured to form an insulating layer, that is, an insulating layer that later becomes an “interlayer insulating layer”.
The heat curing conditions are selected in the range of 150 to 220 ° C. for 20 to 80 minutes, and more preferably in the range of 160 to 200 ° C. for 30 to 120 minutes. When a support subjected to a release treatment is used, the support may be peeled off after thermosetting.
Further, the heat curing may be divided into two stages, and after heating for about 30 minutes at 150 ° C. or less, it may be cured by heating at 160 to 200 ° C. for 30 to 120 minutes.

After forming an insulating layer by said method, you may pass through a drilling process (3) as needed. The drilling step (3) is a step of drilling the circuit board and the formed insulating layer by a method such as drill, laser, plasma, or a combination thereof to form a via hole, a through hole, or the like. As the laser, a carbon dioxide laser, YAG laser, UV laser, excimer laser, or the like is used.
The support may be peeled off after this step (3). In recent years, in order to increase the intensity of the laser and perform drilling in a short time, with the support attached, there is a tendency to perform drilling using a carbon dioxide gas laser and peel the support film after drilling There is.

In the roughening treatment step (4), the surface of the insulating layer is roughened with an oxidizing agent. Further, when via holes, through holes, and the like are formed in the insulating layer and the circuit board, so-called “smear” generated when these are formed may be removed by an oxidizing agent. Roughening and smear removal can be performed simultaneously.
Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, nitric acid and the like. Among these, an alkaline permanganate solution (for example, potassium permanganate, sodium permanganate hydroxide), which is an oxidizing agent widely used for roughening an insulating layer in the production of multilayer printed wiring boards by the build-up method. Sodium aqueous solution) can be used.
By roughening, irregular anchors are formed on the surface of the insulating layer.

In the conductor layer forming step (5), a conductor layer is formed by plating on the surface of the insulating layer that has been roughened and formed with uneven anchors.
Examples of the plating method include an electroless plating method and an electrolytic plating method. The metal for plating is not particularly limited as long as it can be used for plating.
It is also possible to adopt a method in which a plating resist having a pattern opposite to that of the conductor layer (wiring pattern) is formed first, and then the conductor layer (wiring pattern) is formed only by electroless plating.
After forming the conductor layer, an annealing treatment may be performed at 150 to 200 ° C. for 20 to 90 minutes. By performing the annealing treatment, the adhesive strength between the interlayer insulating layer and the conductor layer tends to be further improved and stabilized.
In the circuit forming step (6), a known method such as a subtractive method or a semi-additive process (SAP) can be used as a method for patterning the conductor layer and forming a circuit.

  The surface of the conductor layer thus produced may be roughened. By roughening the surface of the conductor layer, the adhesion with the resin in contact with the conductor layer tends to be improved. In order to roughen the conductor layer, organic acid micro-etching agents “CZ-8100”, “CZ-8101”, “CZ-5480” (all trade names, manufactured by MEC Co., Ltd.) and the like can be used. .

The circuit board used for the multilayer printed wiring board of the present invention is not particularly limited, but on one or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, Examples include a conductor layer (circuit) that has been patterned.
Moreover, the multilayer printed wiring board which has the conductor layer (circuit) by which the conductor layer and the insulating layer were alternately formed, and was patterned on the single side | surface or both surfaces, from the resin film of this invention on the single side | surface or both surfaces of the said circuit board Having a formed interlayer insulation layer, having a conductor layer (circuit) patterned on one or both sides thereof, a cured product formed by laminating and curing the resin film of the present invention (as a layer structure, adhesion An auxiliary layer, a resin composition layer for an interlayer insulating layer, a resin composition layer for an interlayer insulating layer, and a bonding auxiliary layer in this order) have a conductor layer (circuit) patterned on one or both sides of the present invention. In the circuit board.
From the viewpoint of adhesion of the interlayer insulating layer to the circuit board, the surface of the conductor layer of the circuit board may be subjected to a roughening process in advance by a blackening process or the like.

[Prepreg]
It is also possible to obtain a prepreg containing the resin composition of the present invention by impregnating the fiber base material with the resin composition of the present invention.
The method for impregnating the fiber base material with the resin composition is not particularly limited, and examples thereof include a hot melt method and a solvent method.
The hot melt method is a method in which a resin composition is coated on a coated paper having good releasability from the resin composition without dissolving the resin composition in an organic solvent, and then laminated on a textile material, or a resin composition In this method, the product is directly applied to the sheet-like reinforcing substrate by a die coater or the like without dissolving the product in an organic solvent.
The solvent method is a method in which a resin composition is dissolved in an organic solvent to prepare a varnish, and the fiber base material is impregnated with the varnish.
Although it does not specifically limit as drying conditions after an impregnation, For example, the resin composition of this invention is contained by heat-drying for 1 to 10 minutes at the temperature of 80-180 degreeC, and semi-hardening (B stage-izing). A prepreg can be obtained.

As a fiber base material, the well-known thing used for the laminated board for various electrical insulation materials can be used.
Examples of the material of the fiber substrate include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. In applications other than those for electrical insulating materials, it is also possible to use carbon fibers or the like used for fiber reinforced substrates.
Examples of the shape of the fiber base material include woven fabrics, nonwoven fabrics, robinks, chopped strand mats, and surfacing mats.
The material and shape of the fiber base material may be selected according to the use, performance, etc. of the prepreg, and can be used alone or in combination of two or more kinds of materials and shapes.
The thickness of the fiber substrate is preferably 0.01 to 0.5 mm, more preferably 0.01 to 0.2 mm, and still more preferably 0.01 to 0.1 mm.
From the viewpoint of heat resistance, moisture resistance, and processability, the fiber base material may be one that has been surface-treated with a silane coupling agent or the like or one that has been mechanically subjected to fiber opening treatment.

  The prepreg containing the resin composition of the present invention may include the adhesion auxiliary layer described in the section of the resin film of the present invention. The suitable aspect and formation method of an adhesion auxiliary layer are the same as the case in the resin film of this invention.

Next, an example of a method for producing a multilayer printed wiring board using a prepreg will be described.
A single prepreg or a plurality of prepregs are stacked on a circuit board, sandwiched between metal plates through a release film, and laminated by pressing under pressure and heating conditions. When stacking a plurality of prepregs, when the prepreg has an adhesion auxiliary layer, it is preferable to laminate the prepreg so that the adhesion auxiliary layer is formed on the outside. The pressurization and heating conditions are not particularly limited. For example, the press lamination can be performed at a pressure of 5 to 40 kgf / cm ² and a temperature of 120 to 200 ° C. for 20 to 100 minutes.
Similarly to the resin film of the present invention, the prepreg may be laminated on a circuit board by a vacuum laminating method and then heat-cured. Then, after roughening the surface of the cured prepreg in the same manner as described in the section of the multilayer printed wiring board of the present invention, a conductor layer is formed by plating to produce a multilayer printed wiring board. it can.

[1] Next, the first invention will be described in more detail with reference to examples. However, the first invention is not limited to these examples.

Example 1
As an epoxy resin, 25.8 parts by mass of “NC-3000-H” (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration: 100% by mass), which is a biphenyl novolac type epoxy resin,
6.3 parts by mass of “PAPS-PN2” (manufactured by Asahi Organic Materials Co., Ltd., trade name, solid content concentration: 100% by mass, Mw / Mn = 1.17) as a novolak type phenolic resin,
As an epoxy resin curing agent, 4.9 parts by mass of “LA-1356-60M” (trade name, solvent: MEK, solid content concentration 60% by mass, manufactured by DIC Corporation), which is a triazine-modified phenol novolac resin,
As an inorganic filler, the surface of “SO-C2” (manufactured by Admatechs Co., Ltd., trade name, average particle size: 0.5 μm) was treated with an aminosilane coupling agent, and further silica (solid) dispersed in MEK. 92.9 parts by mass of a partial concentration of 70% by mass)
As a curing accelerator, 0.026 parts by mass of “2E4MZ” (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name, solid content concentration: 100% by mass), which is 2-ethyl-4-methylimidazole,
As an additional solvent, 13.1 parts by mass of MEK was blended and subjected to mixing and bead mill dispersion treatment to prepare a resin composition varnish 1 for an adhesive film.
The resin composition varnish 1 for an adhesive film obtained above was applied onto a support film PET (manufactured by Teijin DuPont Films, trade name: G2, film thickness: 50 μm), and then dried to obtain a resin. A composition layer was formed. The coating thickness was 40 μm and drying was performed so that the residual solvent in the resin composition layer was 8.0% by mass. After drying, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name: NF-13, thickness: 25 μm) was laminated as a protective film on the resin composition layer surface side. Then, the obtained film was wound up in roll shape and the adhesive film 1 was obtained.

Examples 2 to 6, 8 and Comparative Examples 1 to 6
In Example 1, adhesive films 2 to 6 and 8 to 14 were obtained in the same manner as in Example 1 except that the raw material composition and production conditions were changed as described in Table 1.

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

The resin varnish A used above was produced by the following procedure.
As an epoxy resin, 63.9 parts by mass of “NC-3000-H” (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration: 100% by mass), which is a biphenyl novolac type epoxy resin,
As an epoxy resin curing agent, 18.0 parts by mass of “LA-1356-60M” (trade name, solvent; MEK, solid content concentration 60% by mass, manufactured by DIC Corporation), which is a triazine-modified phenol novolac resin,
15.2 parts by mass of “EXL-2655” (trade name, manufactured by Rohm and Haas Electronic Materials Co., Ltd.), which is a core-shell rubber particle,
As an inorganic filler, 8.8 parts by mass of fumed silica “Aerosil R972” (manufactured by Nippon Aerosil Co., Ltd., trade name, average particle size: 0.02 μm, solid content concentration: 100% by mass),
As a curing accelerator, 1.28 parts by mass of “2E4MZ” (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name, solid concentration 100% by mass), which is 2-ethyl-4-methylimidazole,
As an additional solvent, 226.1 parts by mass of cyclohexanone was blended and subjected to mixing and bead mill dispersion treatment to prepare a resin varnish A.
The resin varnish A obtained above was applied to PET (Teijin DuPont Films, trade name: G2, film thickness: 50 μm) as a support film so as to have a film thickness of 10 μm, and then dried. Thus, a support film 2 having a film thickness of 60 μm was obtained.

Next, the resin composition varnish for an adhesive film applied on the support film 2 obtained above was produced in the same manner as in Example 1 with the raw material composition and production conditions shown in Table 1.
The adhesive film 7 was obtained in the same manner as in Example 1 using the support film 2 and the resin composition varnish for adhesive film.

[Evaluation method]
The obtained adhesive films 1 to 14 were evaluated by the following methods.

(Preparation and test method for adhesive film handling test)
The obtained adhesive films 1 to 14 were cut into a size of 500 mm × 500 mm, and Samples 1 to 14 for handling test of the adhesive film were produced.
Using the samples 1 to 14 for handling test of the produced adhesive film, the handling was evaluated by the following methods (1) to (3). “Anything that was not defective in any of the tests was regarded as“ good handling ”.
(1) About the samples 1-14 for the handleability test of an adhesive film, the protective film was peeled first. When the protective film was peeled off, a part of the applied and dried resin that adhered to the protective film side or a powder that had fallen off was regarded as poor handleability.
(2) A film having two points at the center of the film (two points at the end so as to be 500 mm × 250 mm) and cracking occurred in the applied and dried resin was defined as poor handleability.
(3) "MCL-E-679FG (R)" which is a copper clad laminate obtained by blackening and reducing the surface copper foil (manufactured by Hitachi Chemical Co., Ltd., copper foil thickness 12 μm, plate thickness 0.41 mm) In addition, lamination was performed by lamination using a batch type vacuum pressure laminator “MVL-500” (trade name, manufactured by Meiki Seisakusho Co., Ltd.). The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa. After cooling to room temperature, the support film was peeled off (the adhesive film 7 was peeled between PET and the resin layer formed thereon on the support film 2). In this case, a material in which powder falling off or PET was torn in the middle was regarded as poor handleability.

(Preparation and test method of thermal expansion coefficient measurement sample)
Each of the obtained adhesive films 1 to 14 was cut into a size of 200 mm × 200 mm, the protective film was peeled off, and a batch-type vacuum pressure laminator “MVL-500” (Meiki Seisakusho Co., Ltd.) was applied to a 18 μm thick copper foil. And product name). The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 90 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film is peeled off (for the adhesive film 7, the support film 2 was peeled between PET and the resin layer formed thereon) and cured in a 180 ° C. drier for 120 minutes. did. Thereafter, the copper foil was removed with a ferric chloride solution, and samples cut into a width of 3 mm and a length of 8 mm were used as samples 1 to 14 for measuring the thermal expansion coefficient.

The thermal expansion coefficient was measured by the following method using the produced samples 1 to 14 for measuring the thermal expansion coefficient.
Using the thermomechanical analyzer manufactured by Seiko Instruments Inc., the obtained samples 1 to 14 for measuring the thermal expansion coefficient were heated to 240 ° C. at a heating rate of 10 ° C./min, cooled to −10 ° C. A change curve of the expansion amount when the temperature was raised to 300 ° C. at a temperature rate of 10 ° C./min was obtained, and an average coefficient of thermal expansion of 0 to 150 ° C. of the change curve of the expansion amount was obtained.

(Preparation and test method of embedding evaluation board)
The inner layer circuit used for the embedding evaluation board is as follows. “MCL-E-679FG (R)” (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a copper clad laminate having a copper foil thickness of 12 μm and a plate thickness of 0.15 mm (including the copper foil thickness), has a diameter of 0. A 15 mm through hole was produced by a drilling method so as to be a group of 25 × 25 at 5 mm intervals. Next, desmearing and electroless plating were performed, and electrolytic plating was performed in the through holes using electrolytic plating.
As a result, a circuit board having a plate thickness including copper thickness of 0.2 mm, a diameter of 0.1 mm, and 25 × 25 through holes at intervals of 5 mm was obtained.
Next, after arranging the adhesive films 1 to 14 with the protective film peeled off so that the resin composition layer faces the circuit surface side of the circuit board, a batch-type vacuum laminator “MVL-500” (name machine Co., Ltd.) (Product name, manufactured by Seisakusho Co., Ltd.). The degree of vacuum 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, a circuit board having through holes with adhesive films on both sides was sandwiched between two aluminum plates having a thickness of 1 mm, and lamination was performed using the vacuum laminator. The degree of 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 is peeled off (for the adhesive film 7, the support film 2 was peeled between PET and the resin layer formed thereon) and cured in a 180 ° C. drier for 120 minutes. did. Thus, embedding evaluation substrates 1 to 14 were obtained.

Using the fabricated embedding evaluation substrates 1 to 14, embedding properties were evaluated by the following method.
Using a contact-type surface roughness meter “SV2100” (trade name) manufactured by Mitutoyo Corporation, the steps on the surface of the through-hole portions of the embedding property evaluation boards 1 to 14 were measured. The level difference was measured so that 10 central portions of the surface of the through hole could enter, and the average value of the 10 dents was calculated.

The ingredients in Table 1 are shown below.
[Epoxy resin]
NC-3000-H: biphenyl novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration 100% by mass)
[Novolac type phenolic resin]
PAPS-PN2: novolak type phenol resin (Asahi Organic Materials Co., Ltd., trade name, solid content concentration 100% by mass, Mw / Mn = 1.17)
PAPS-PN3: Novolak type phenol resin (Asahi Organic Materials Co., Ltd., trade name, solid content concentration 100% by mass, Mw / Mn = 1.50)
HP-850: Novolac-type phenolic resin manufactured using hydrochloric acid instead of phosphoric acid (manufactured by Hitachi Chemical Co., Ltd., trade name, solid content concentration 100% by mass)
[Triazine-modified phenol novolac resin]
LA-1356-60M: triazine-modified phenol novolac resin (manufactured by DIC Corporation, trade name, solvent; MEK, solid content concentration 60 mass%)
[Inorganic filler]
SO-C2: Silica “SO-C2” (trade name, average particle size: 0.5 μm) manufactured by Admatechs Co., Ltd., treated with an aminosilane coupling agent and further dispersed in a MEK solvent (Solid concentration 70% by mass)
SO-C6: Silica “SO-C6” (trade name, average particle size: 2.2 μm) manufactured by Admatechs Co., Ltd., treated with an aminosilane coupling agent and further dispersed in a MEK solvent (Solid concentration 70% by mass)
Aerosil R972: fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name, solid content concentration 100% by mass, specific surface area: 100 m ² / g)
[Curing accelerator]
2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name, solid content concentration 100% by mass)

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

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

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

[Synthesis of cyanate prepolymer]
Production Example 1
(Synthesis of cyanate prepolymer A)
In a 5 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, “AroCy B-10”, a bisphenol A type bifunctional cyanate resin (manufactured by Huntsman, trade name, molecular weight) 278), p- (α-cumyl) phenol (paracumylphenol) (trade name, molecular weight 212, manufactured by Mitsui Chemicals Fine Co., Ltd.), 45.8 g, and 1303 g of toluene were added to obtain a reaction solution. The temperature of the reaction solution was raised and stirred until the temperature of the reaction solution reached 90 ° C. When the temperature reached 90 ° C., 2.799 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., trade name, solid content concentration 8 mass%, mineral spirit solution cut product) was added to the reaction solution. Thereafter, the temperature was further raised to 110 ° C., and the mixture was stirred at 110 ° C. for 180 minutes. Subsequently, cyanate prepolymer A (weight average molecular weight: 8230) dissolved in toluene (hereinafter simply referred to as “prepolymer A”) was added by further adding toluene so that the solid content concentration of the reaction solution was 70% by mass. Said).

[Method for producing adhesion auxiliary layer with support]
Production Example 2
After blending each component shown in Table 2, the resin component was stirred until dissolved, and dispersed by bead mill treatment to obtain a varnish for an auxiliary adhesion layer.
The adhesion auxiliary layer varnish obtained above is coated on a 38 μm-thick release PET film using a die coater and dried at 130 ° C. for 2 minutes, whereby the film thickness of the adhesion auxiliary layer is obtained. Obtained an auxiliary adhesion layer with a support of 4 μm. The raw materials used are shown in Table 2.

The materials used for blending the resin varnish for the adhesion auxiliary layer are shown below.
[(I) component]
NC-3000-H: a novolak type epoxy resin containing a biphenyl aralkyl structure (manufactured by Nippon Kayaku Co., Ltd., trade name, solid content concentration: 100% by mass, epoxy equivalent: 289 g / eq)
[(J) component]
BA230S75: Cyanate resin prepolymer “Primaset BA230S75” (Lonza, trade name, solid content 75% by mass, MEK cut product)
[(K) component]
Aerosil R972: fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name, solid content concentration 100% by mass, specific surface area: 100 m ² / g)
[(M) component]
BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (manufactured by Nippon Kayaku Co., Ltd., trade name, solid concentration 100 mass%, number average molecular weight: 26000, weight average molecular weight: 110000). BPAM-155 was added in a state of being dissolved in dimethylacetamide so that the solid content concentration was 10% by mass in advance.
[(N) component]
YX1256B40: Phenoxy resin (Mitsubishi Chemical Corporation, trade name, solid concentration 40% by mass, MEK cut product)
[Curing accelerator]
Curing accelerator 1: addition reaction product of tributylphosphine and 1,4-benzoquinone synthesized with reference to JP 2011-179008 A (solid content concentration: 100% by mass)

[Preparation of resin film for interlayer insulation layer]
Reference example 1
After blending each component shown in Table 3, the mixture was stirred until the resin component was dissolved. Subsequently, it disperse | distributed by the bead mill process and the resin composition varnish 1 for interlayer insulation layers was obtained.
Next, on the adhesion auxiliary layer of the adhesion auxiliary layer with support obtained in Production Example 2, the interlayer insulating layer resin composition varnish 1 was applied using a die coater, and the mixture was heated at 100 ° C. for 1.5 minutes. By drying, the resin composition layer for interlayer insulation layers whose film thickness is 36 micrometers was formed, and the resin film 1 for interlayer insulation layers was obtained.

Reference Examples 2 to 10 and Comparative Reference Examples 1 to 5
A resin film for an interlayer insulating layer was obtained in the same manner as in Reference Example 1 except that the composition of the resin composition varnish for the interlayer insulating layer was changed to the composition shown in Table 3 in Reference Example 1.

  Using the resin film obtained in each example, various tests were conducted according to the following methods and evaluated.

(Appearance evaluation after curing with support)
Appearance evaluation after curing with a support (PET) was performed according to the following procedure.
First, after cutting out the resin film obtained in each example into a 200 mm square, the protective film is peeled off, and the resin composition layer for the interlayer insulating layer is disposed so as to face the circuit surface of the printed wiring board, and then laminated. It was.
The printed wiring board is a copper-clad laminate “MCL-E-679FG” (trade name, manufactured by Hitachi Chemical Co., Ltd.) having a copper layer with a thickness of 35 μm. A circuit processed product was used.
The laminating apparatus is a vacuum pressurizing laminator “MVLP-500 / 600IIA” (trade name, manufactured by Meiki Seisakusho Co., Ltd.), evacuated at 110 ° C. for 30 seconds, and then applied at 0.5 MPa for 30 seconds. Pressed. Thereafter, hot pressing was performed at 110 ° C. for 60 seconds and at 0.5 MPa.
Next, after cooling to room temperature, with the PET film as a support attached, curing was performed in an explosion-proof dryer at 130 ° C. for 20 minutes, then at 180 ° C. for 40 minutes, and appearance evaluation after curing with the support A substrate was produced.
Appearance evaluation is performed visually. “OK” indicates that no voids or peeling is observed between the interlayer insulating layer and the printed wiring board on the front and back of the evaluation board, and “NG” indicates that there is one or more voids or peeling. " The results are shown in Table 3.

(Smear removal evaluation method)
The resin film obtained in each example was evaluated for smear (resin residue) removability according to the following procedures (1) to (6). The results are shown in Table 3.

(1) Production of Circuit Board Double-sided copper-clad laminate of glass cloth base epoxy resin (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-700G (R), copper foil thickness 12 μm, base material thickness 0. 4 mm), a circuit pattern was formed by etching, and a roughening treatment was performed using “MEC Etch Bond C (registered trademark) CZ8101” manufactured by MEC Co., Ltd. Furthermore, a rust prevention treatment was performed using “MEC Etch Bond (registered trademark) CL-8301” manufactured by MEC Co., Ltd. This produced the circuit board.
(2) Laminating method of resin film The protective film is peeled off from the resin film produced in each example, and the resin composition layer for the interlayer insulating layer is disposed on the circuit surface side of the circuit board. Using “MVLP-500” (trade name, manufactured by Meiki Seisakusho Co., Ltd.), it was laminated on both surfaces of the circuit board produced in (1). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 15 hPa or less, and then pressure bonding at 100 ° C. for 30 seconds at a pressure of 0.5 MPa.
(3) Formation of interlayer insulation layer After cooling the sample obtained in (2) to room temperature, the support (PET film) was peeled off. Thereafter, heating was performed at 130 ° C. for 20 minutes, and then at 180 ° C. for 40 minutes to cure the resin composition layer for an interlayer insulating layer to form an interlayer insulating layer.
(4) Via hole formation method Using a CO ₂ laser processing machine “LC-2F21B” manufactured by Via Mechanics Co., Ltd., processing the interlayer insulating layer in a burst mode with a frequency of 2000 kHz, a pulse width of 15 μs, and a shot number of 4 A via hole having a via hole top diameter (diameter) of 70 μm on the surface of the interlayer insulating layer and a via hole bottom diameter of 60 μm on the bottom surface of the interlayer insulating layer was formed (taper rate (via bottom / via top) is about 86%).
(5) Desmear treatment method The sample obtained in (4) was immersed in a swelling liquid “Swelling Dip Securigant P” (manufactured by Atotech Japan Co., Ltd.) heated to 70 ° C. for 10 minutes. Next, it was immersed for 10 minutes in the roughening solution “Concentrate Compact CP” (manufactured by Atotech Japan Co., Ltd.) heated to 80 ° C., and subsequently neutralized “Reduction Securigant P500” (40 ° C.) ( The solution was neutralized by immersion in Atotech Japan Co., Ltd. for 5 minutes. Thus, a desmeared substrate was obtained.
(6) Evaluation method of smear removability The periphery of the via hole bottom after desmear treatment was observed using a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., trade name: S-4700), and from the obtained image The maximum smear length from the wall surface at the bottom of the via hole was measured.

(Dielectric loss tangent)
The resin film obtained in each example was thermally cured by heating at 190 ° C. for 90 minutes, and then the support was peeled to obtain a sheet-like cured product. A sample obtained by cutting the cured product into a length of 80 mm and a width of 2 mm was used as an evaluation sample. The dielectric loss tangent of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. The results are shown in Table 3.

(Reflow heat resistance evaluation method)
About each resin film for interlayer insulation layers, reflow heat resistance was evaluated in the following procedures. The results are shown in Table 3.
(1) Production of Circuit Board Double-sided copper-clad laminate of glass cloth base epoxy resin (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-700G (R), copper foil thickness 12 μm, base material thickness 0. 4 mm), a circuit pattern was formed by etching, and a roughening treatment was performed using “MEC Etch Bond C (registered trademark) CZ8101” manufactured by MEC Co., Ltd. Furthermore, a rust prevention treatment was performed using “MEC Etch Bond (registered trademark) CL-8301” manufactured by MEC Co., Ltd. This produced the circuit board. The remaining copper ratio of the circuit pattern was 80 to 100%.
(2) Laminating method of resin film The protective film is peeled off from the resin film produced in each example, and the resin composition layer for the interlayer insulating layer is disposed on the circuit surface side of the circuit board. Using “MVLP-500” (trade name, manufactured by Meiki Seisakusho Co., Ltd.), it was laminated on both surfaces of the circuit board produced in (1). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 15 hPa or less, and then pressure bonding at 100 ° C. for 30 seconds at a pressure of 0.5 MPa.
(3) Formation of interlayer insulating layer After cooling the sample obtained in (2) to room temperature, with the support (PET film) attached, it was heated at 130 ° C for 20 minutes, then at 180 ° C for 40 minutes, The resin composition layer for an interlayer insulating layer was cured to form an interlayer insulating layer. After curing, the support was peeled off.
(4) Desmear treatment method The sample obtained in (3) was immersed in a swelling solution “Swelling Dip Securigant P” (manufactured by Atotech Japan Co., Ltd.) heated to 70 ° C. for 10 minutes. Next, it was immersed in a roughening solution “Concentrate Compact CP” (manufactured by Atotech Japan Co., Ltd.) heated to 80 ° C. for 20 minutes, and subsequently neutralized solution “Reduction Securigant P500” (40 ° C.) ( The solution was neutralized by immersion in Atotech Japan Co., Ltd. for 5 minutes.
(5) Electroless plating and electroplating Dipping treatment at 60 ° C. for 5 minutes in “Cleaner Secure Gantt 902” (manufactured by Atotech Japan Co., Ltd.) as a cleaner, then “Predip Neo Gantt B” (Atotech Japan Co., Ltd.) as a pre-dip (Made by company) for 2 minutes at 25 ° C, "Activator Neo Gantt 834" as a seeder for 5 minutes at 40 ° C, "Reducer Neogant WA" as a reducer for 5 minutes at 30 ° C, "MSK-DK" as electroless plating Was subjected to an immersion treatment at 30 ° C. for 30 minutes to form an electroless plating layer having a thickness of 200 to 250 nm. Further, an electroplating layer having a plating thickness of 25 to 30 μm was formed in a copper sulfate plating bath at a current density of ² A / dm ² .
Next, the obtained electroplated substrate was cut into 40 mm squares, and 10 heat resistance evaluation substrates were produced.
As the reflow device, an air reflow system (model number: TAR-30-366PN) manufactured by Tamura Seisakusho Co., Ltd. was used, and the reflow device set to a maximum of 260 ° C. was used. The heat resistance evaluation substrate obtained above was passed through a reflow apparatus 200 times at maximum, and the number of passes until swelling occurred was examined, and the average value of 10 samples was taken as the average number of reflow passes.

The components in Table 3 are shown below.
[(A) component]
N673: Cresol novolac type epoxy resin “Epiclon (registered trademark) N673” (manufactured by DIC Corporation, trade name, epoxy equivalent: 210 g / eq, solid content concentration: 100 mass%)
NC-7000-L: Novolac type epoxy resin containing naphthalene skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name, solid concentration 100 mass%, epoxy equivalent: 231 g / eq)
840S: Bisphenol A type liquid epoxy resin “Epiclon (registered trademark) 840S” (manufactured by DIC Corporation, trade name, solid content concentration 100 mass%, epoxy equivalent: 185 g / eq)
[Component (b)]
-BA230S75: Cyanate resin prepolymer (Lonza, trade name, solid concentration 75% by mass, MEK cut product)
Cyanate prepolymer A: Cyanate prepolymer A synthesized in Production Example 1 (solid content concentration 70% by mass)
[Component (c)]
-HPC-8000-65T: Active ester curing agent (manufactured by DIC Corporation, trade name, active ester equivalent: 223 g / eq, solid content concentration 65% by mass, toluene cut product)
[Component (d)]
Curing accelerator 1: addition reaction product of tributylphosphine represented by the following formula (d-1) and 1,4-benzoquinone synthesized with reference to JP 2011-179008 A (solid content concentration: 100% by mass)

  Curing accelerator 2: Tris (p-methylphenyl) phosphine represented by the following formula (d-2) synthesized with reference to JP 2011-179008 A and an addition reaction product of 1,4-benzoquinone (solid (Minute concentration 100% by mass)

[Other curing accelerators]
2PZ-CN: 1-cyanoethyl-2-phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd., solid content concentration: 100% by mass)
DMAP: N, N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration 100% by mass)
[(E) component]
Vinyl silane-treated silica: “SO-C2” (spherical silica treated with a vinyl silane coupling agent) (manufactured by Admatechs, trade name, volume average particle size 0.5 μm, solid content concentration 100 mass%)
Epoxy silane treated silica: “SO-C2” which is spherical silica treated with an epoxy silane coupling agent (manufactured by Admatechs, trade name, volume average particle size 0.5 μm, solid content concentration 100 mass%)
Aminosilane-treated silica: “SO-C2” which is a spherical silica treated with an aminosilane coupling agent (manufactured by Admatechs, trade name, volume average particle size 0.5 μm, solid content concentration 100 mass%)
[Component (f)]
・ Dicyandiamide: (Nippon Carbite Industries, Ltd., solid content concentration: 100% by mass)
[(G) component]
YX1256B40: Phenoxy resin (Mitsubishi Chemical Corporation, trade name, solid concentration 40% by mass, MEK cut product)
[(H) component]
BYK330: Resin having a siloxane skeleton (manufactured by Big Chemie Japan, trade name, solid content concentration 25% by mass, xylene cut product)

From the results of Table 3, the interlayer insulating layer formed by the resin film for interlayer insulating layers obtained in Reference Examples 1 to 10 is excellent in appearance even when cured with a support (PET), and has a good smear. It showed removability. It was also found that the dielectric loss tangent is small and the heat resistance is sufficient.
On the other hand, the interlayer insulation layer formed with the resin film for interlayer insulation layers obtained by Comparative Reference Examples 1-5 was inferior in any characteristic.

The resin composition of the present invention provides an interlayer insulating layer having a good appearance even when cured with a support, having a low dielectric loss tangent, excellent smear-removability and heat resistance after laser processing, and the interlayer insulating layer A multilayer printed wiring board including layers is obtained.
Therefore, the resin composition of the present invention can be widely used for electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes.

Claims (1)

(A) a novolak-type phenol resin having a dispersion ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 1.1 to 1.7;
(B) an epoxy resin;
(C) an inorganic filler;
(D) a solvent;
A resin composition layer formed by layering a resin composition containing
(B) the epoxy resin is at least one novolak type epoxy resin selected from the group consisting of a novolak type epoxy resin having a biphenyl skeleton, a cresol novolak type epoxy resin and an aralkyl novolak type epoxy resin;
(C) The average particle size of the inorganic filler is 0.1 μm or more, and the content in the resin composition layer is 20 to 95% by mass in the resin solid content,
The adhesive film for multilayer printed wiring boards whose content of (D) solvent in a resin composition layer is 1-20 mass%.