JP2017193691A - Adhesive film for multilayer printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive film for a multilayer printed board excellent in embedding property of unevenness even when a silica filler is highly filled.SOLUTION: An adhesive film for a multilayer printed board has a resin composition layer obtained by layer formation of a resin composition containing (A) a novolak-based phenolic resin having a dispersion ratio (Mw/Mn) between a weight average molecular weight (Mw) of a number average molecular weight (Mn) of 1.05-1.8, (B) an epoxy resin represented by a general formula (1) and (C) an inorganic filler, on a support film, where an average particle size of (C) the inorganic filler in the resin composition layer is 0.1 μm or more, and a content of (C) the inorganic filler is 20-95 mass% in a resin solid content.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.

  In the build-up manufacturing technique, the interlayer insulating layer and the wiring layer are manufactured by a resin composition for forming the interlayer insulating layer (hereinafter also referred to as “resin composition for interlayer insulating layer”), a wiring layer, and the like. The copper foil for forming the film is pressed for a long time at a high temperature using a pressing device to thermally cure the resin composition for the interlayer insulating layer, and after obtaining an interlayer insulating layer having a copper foil, it is necessary A method of forming wiring using a so-called “subtractive method” in which via holes for interlayer connection are formed using a drill method, a laser method, etc., and then a copper foil is removed by etching leaving a necessary portion. However, it has been common in the past.

  However, in accordance with the demands for reducing the size and weight of the multilayer printed wiring board as described above, increasing the density of the wiring, etc., the resin composition for the interlayer insulating layer and the copper foil are quickly used at a high temperature using a vacuum laminator. After pressurization, the interlayer insulating layer resin composition is thermally cured at a high temperature using a dryer, etc., and via holes for interlayer connection are formed using a drill method, a laser method, etc. as necessary, and a plating method Therefore, a so-called “additive method” in which a wiring layer is formed in a necessary portion has attracted attention.

  The resin composition for an interlayer insulating layer used in the build-up method includes an aromatic epoxy resin and a curing agent having active hydrogen for the epoxy resin (for example, a phenolic curing agent, an amine curing agent, a carboxylic acid type). A combination of a curing agent and the like 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. Moreover, when these hardening | curing agents were used, the problem that the storage stability of the resin composition was impaired had arisen.

On the other hand, it is known that a cyanate compound having a thermosetting cyanate group gives a cured product having excellent electric characteristics. However, the reaction in which the cyanato group forms an S-triazine ring by thermal curing requires, for example, curing at a high temperature of 230 ° C. for 120 minutes or more for a relatively long time. It was unsuitable as a resin composition for interlayer insulation layers for printed wiring boards.
As a method for lowering the curing temperature of the cyanate compound, a method is known in which a cyanate compound and an epoxy resin are used in combination and cured using a curing catalyst (see, for example, Patent Documents 1 and 2).

  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).

JP2013-40298A JP 2010-90237 A JP-T-2006-527920 JP 2007-87982 A JP 2009-280758 A

[A] When the silica filler is made high in order to reduce the CTE of the build-up layer, the build-up material tends to make it difficult to bury the unevenness of the wiring pattern of the inner layer circuit. 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.

[B] Moreover, in the conventional resin composition for multilayer printed wiring boards, after coating on the support or adhesion auxiliary layer, repellency may occur on the support or adhesion auxiliary layer. Adjustment may be difficult. In particular, when the resin film is cured, it is required to cure with the support attached in order to prevent contamination of impurities such as dust. Mold processing is often performed. In this case, repelling is more likely to occur. Further, according to the study by the present inventors, depending on the type of curing agent to be used, for example, in the case of a resin composition containing an active ester curing agent, repelling may be more likely to occur. There was found. According to further studies by the present inventors, it has been found that repelling may be more likely to occur even in the case of a resin composition containing an inorganic filler that has undergone a specific surface treatment.
In order to avoid such repelling, when trying to avoid the use of a specific curing agent that contributes to the increase of repelling and an inorganic filler that has been subjected to a specific surface treatment, various properties such as reflow heat resistance are exhibited. There was a problem of lowering, and it was difficult to achieve both.
Furthermore, a resin film for an interlayer insulating layer is required that has a small surface roughness after desmearing and is excellent in adhesive strength with a conductor layer.

  The second invention is made in order to solve such a problem, and after coating on the support or the adhesion auxiliary layer, repellency hardly occurs on the support or the adhesion auxiliary layer, and It aims at providing the thermosetting resin composition (resin composition for interlayer insulation layers) excellent in reflow heat resistance. Furthermore, providing the resin film for interlayer insulation layers formed using this thermosetting resin composition, the resin composition layer for interlayer insulation layers which consists of this resin film for interlayer insulation layers, and an adhesion auxiliary layer Provided is a multilayer resin film having a small surface roughness after desmearing and having excellent adhesive strength with a conductor layer, at least one selected from the group consisting of the resin film for an interlayer insulating layer and the multilayer resin film It aims at providing the multilayer printed wiring board obtained using this, and its manufacturing method.

[A] 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 phenol 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 1.05 to 1.8 of a weight average molecular weight (Mw) and a number average molecular weight (Mn); A resin composition layer formed by layering a resin composition containing an epoxy resin represented by formula (1) and an inorganic filler (C) on a support film, the resin composition layer (C) The average particle size of the inorganic filler is 0.1 μm or more, and the content of the (C) inorganic filler is 20 to 95% by mass of the resin solid content. Adhesive film.

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

[B] As a result of intensive studies to solve the second problem, the present inventors have found that the second problem can be solved by the following specific resin composition, and complete the present invention. It came to. That is, the second invention provides the following [1] to [20].

[1] A thermosetting resin composition comprising (a) an epoxy resin, (b) a curing agent, (c) an inorganic filler, and (d) a resin having a polysiloxane skeleton,
The content of the inorganic filler (c) is 50 to 90% by mass with respect to the solid content of the thermosetting resin composition,
(D) The thermosetting resin composition whose content of resin which has a polysiloxane skeleton is 0.01-1 mass% with respect to solid content of a thermosetting resin composition.
[2] The thermosetting according to the above [1], wherein the (b) curing agent contains at least one selected from the group consisting of (b1) an active ester curing agent and (b2) a cyanate curing agent. Resin composition.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the (b) curing agent comprises (b3) a phenol novolac curing agent containing a triazine ring.
[4] The (a) epoxy resin has at least one selected from the group consisting of a bisphenol A type epoxy resin, a naphthalene type epoxy resin, an aralkyl novolak type epoxy resin having a biphenyl skeleton, and a cresol novolak type epoxy resin. The thermosetting resin composition according to any one of [1] to [3].
[5] The thermosetting resin composition according to any one of [1] to [4], wherein the (c) inorganic filler contains silica.
[6] The thermosetting resin composition according to any one of [1] to [5], wherein the inorganic filler (c) contains surface-treated silica.
[7] The thermosetting resin composition according to any one of [1] to [6], wherein (c) the inorganic filler contains silica surface-treated with an aminosilane coupling agent.
[8] The thermosetting resin composition according to any one of [1] to [7], further comprising (e) a phenoxy resin.
[9] The thermosetting resin composition according to any one of [1] to [8], further including (f) a curing accelerator.
[10] The heat according to [9], wherein (f) the curing accelerator contains at least one organic curing accelerator selected from the group consisting of an organic phosphorus compound, an imidazole compound, and an amine compound. Curable resin composition.
[11] The thermosetting resin composition according to the above [9] or [10], wherein the (f) curing accelerator contains a metal-based curing accelerator.
[12] A resin film for an interlayer insulating layer formed using the thermosetting resin composition according to any one of [1] to [11].
[13] The resin film for an interlayer insulating layer according to [12], which is for forming a buildup layer of a multilayer printed wiring board.
[14] A multilayer resin film comprising a resin composition layer for an interlayer insulating layer comprising the thermosetting resin composition according to any one of the above [1] to [11], and an adhesion auxiliary layer.
[15] A multilayer resin film comprising the interlayer insulating layer resin film according to [12] or the multilayer resin film according to [14], and an organic resin film subjected to a release treatment.
[16] A multilayer print obtained by using at least one selected from the group consisting of the resin film for an interlayer insulating layer according to [12] and the multilayer resin film according to [14] or [15] Wiring board.
[17] A method for producing a multilayer printed wiring board using the multilayer resin film according to the above [15], comprising the following steps.
(1) A step of laminating at least one selected from the group consisting of a resin film for an interlayer insulating layer with a support and a multilayer resin film with a support on one side or both sides of a circuit board.
(2) A step of thermosetting the resin film laminated in step (1) to form an insulating layer.
(3) A step of drilling the circuit board on which the insulating layer is formed in the step (2).
(4) A step of roughening the surface of the insulating layer with an oxidizing agent.
(5) A step of forming a conductor layer by plating on the surface of the roughened insulating layer.
(6) A step of forming a circuit in the conductor layer by a semi-additive method.
[18] The method for producing a multilayer printed wiring board according to the above [17], wherein the support is a support subjected to a release treatment.
[19] The multilayer print according to [18], wherein in the step (2), the resin film laminated in the step (1) is heat-cured with a support subjected to a release treatment attached thereto. A method for manufacturing a wiring board.
[20] The method for producing a multilayer printed wiring board according to the above [18], wherein the support subjected to the release treatment is peeled and removed before any of the steps (2) to (5).
[20] The method for producing a multilayer printed wiring board according to the above [19], wherein the support subjected to the release treatment is peeled and removed before any of the steps (3) to (5).

[A] 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.

[B] According to the second invention, a thermosetting resin composition that hardly repels on the support or adhesion auxiliary layer after coating on the support or adhesion auxiliary layer and has excellent reflow heat resistance. Things can be provided. Moreover, the resin film for interlayer insulation layers which is formed using this thermosetting resin composition and the surface roughness after desmear is small and excellent in adhesive strength with a conductor layer can be provided. Furthermore, it is possible to provide a multilayer resin film comprising a resin composition layer for an interlayer insulation layer comprising the resin film for an interlayer insulation layer and an adhesion auxiliary layer, and the resin film for an interlayer insulation layer and the multilayer resin film The multilayer printed wiring board obtained using at least 1 sort (s) selected from the group which consists of, and its manufacturing method can be provided.

[A] 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 1.05. -1.8 novolak-type phenol resin (hereinafter also simply referred to as “(A) novolak-type phenol resin”) and (B) an epoxy resin represented by the general formula (1) (hereinafter simply referred to as “(B ) Epoxy resin ”) and (C) an inorganic filler, and a resin composition formed by layer-forming a resin film (hereinafter also referred to as“ resin composition for adhesive film ”) on a support film. An average particle size of (C) inorganic filler in the resin composition layer is 0.1 μm or more, and the content of (C) inorganic filler is 20 to 95 of the resin solid content. It is an adhesive film for multilayer printed wiring boards which is mass%.

[Resin composition for adhesive film]
The resin composition for an adhesive film contains (A) a novolak-type phenol resin, (B) an epoxy resin, and (C) an inorganic filler. 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 1.05-1. .8 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.

As a phenol compound used as a raw material, for example, 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 the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 1.05 to 1.8 by the method for producing the 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 novolak type phenol resin having a dispersion ratio (Mw / Mn) of 1.05 to 1.8, preferably 1.1 to 1.7, is produced in a high yield. Can do.

  (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 stock) Cresol novolak resins such as those manufactured by the company and trade names). 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 an epoxy resin represented by the following general formula (1).

  (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.

<Solvent>
It is preferable that the resin composition for adhesive films contains a solvent from a viewpoint of performing layer formation efficiently. 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.

<Residual solvent amount>
The amount of residual solvent in the adhesive film of the present invention varies depending on the material to be handled, but is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and 2 to 10% by mass. Further preferred. 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 when the residual solvent amount is 20% by mass or less, 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 coating and drying the resin composition for adhesive films on a support 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.

[B] Second Invention Next, a thermosetting resin composition, a resin film for an interlayer insulating layer, a multilayer resin film, a multilayer printed wiring board, and a manufacturing method thereof according to the second invention will be described.

The thermosetting resin composition of the present invention (hereinafter sometimes referred to as a resin composition for an interlayer insulating layer) includes (a) an epoxy resin, (b) a curing agent, (c) an inorganic filler, and (d). A thermosetting resin composition containing a resin having a polysiloxane skeleton,
The content of the inorganic filler (c) is 50 to 90% by mass with respect to the solid content of the thermosetting resin composition,
Content of the resin which has the said (d) polysiloxane frame | skeleton is 0.01-1 mass% with respect to solid content of a thermosetting resin composition.
Hereinafter, each component will be described.

<Thermosetting resin composition (resin composition for interlayer insulation layer)>
[(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.
Examples of such (a) epoxy resins include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, a glycidyl ether type epoxy resin is preferable.

(A) Epoxy resins are also classified according to the difference in main skeleton, and in each of the above types of epoxy resins, bisphenol A type epoxy resin (preferably bisphenol A type liquid epoxy resin), bisphenol F type epoxy resin, bisphenol Bisphenol type epoxy resin such as S type epoxy resin; phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin Resin, novolak epoxy resin such as aralkyl novolak epoxy resin; stilbene epoxy resin; triazine skeleton-containing epoxy resin; Is classified into dicyclopentadiene type alicyclic epoxy resin having an epoxy resin and the like; Oren skeleton-containing epoxy resin; naphthalene type epoxy resins; triphenylmethane type epoxy resins; biphenyl type epoxy resin; xylylene type epoxy resin. (A) An epoxy resin may be used individually by 1 type, and may use 2 or more types together.
Examples of the aralkyl novolak type epoxy resin include an aralkyl cresol copolymer novolak type epoxy resin having a naphthol skeleton and an aralkyl novolak type epoxy resin having a biphenyl skeleton.

  Among these, from the viewpoint of reflow heat resistance and the like, at least one selected from the group consisting of bisphenol-type epoxy resins and novolak-type epoxy resins is preferable, and bisphenol A-type epoxy resins, aralkyl novolak-type epoxy resins and bisphenol A novolak-type More preferably, it is at least one selected from the group consisting of epoxy resins. Further, the aralkyl novolac type epoxy resin is more preferably an aralkyl novolak type epoxy resin having a biphenyl skeleton.

(A) When two or more types of epoxy resins are used in combination, a combination of a bisphenol A type epoxy resin and an aralkyl novolak type epoxy resin (particularly, an aralkyl novolak type epoxy resin having a biphenyl skeleton), or a cresol novolak type epoxy A combination of a resin and a bisphenol A novolac epoxy resin is preferred.
When a bisphenol A type epoxy resin and an aralkyl novolak type epoxy resin (particularly an aralkyl novolak type epoxy resin having a biphenyl skeleton) are contained in combination, the content ratio (bisphenol A type epoxy resin / aralkyl novolak type epoxy resin) is: From the viewpoint of reflow heat resistance and the like, 15/85 to 50/50 is preferable, 15/85 to 45/55 is more preferable, and 20/80 to 40/60 is even more preferable.
When used in combination with a cresol novolac type epoxy resin and a bisphenol A novolac type epoxy resin, the content ratio (cresol novolac type epoxy resin / bisphenol A novolak type epoxy resin) is determined according to heat resistance, insulation reliability, and film. 50/50 to 85/15 is preferable, 45/55 to 85/15 is more preferable, and 55/45 to 75/25 is even more preferable.

  Here, the aralkyl novolak type epoxy resin having a biphenyl skeleton means an aralkyl novolak type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, and includes a structural unit represented by the following general formula (a1). An epoxy resin etc. are mentioned.

In general formula (a1), R ^a1 represents a hydrogen atom or a methyl group.

The content of the structural unit represented by the general formula (a1) in the epoxy resin including the structural unit represented by the general formula (a1) is 50 to 100% by mass from the viewpoint of reflow heat resistance and the like. Is preferable, it is more preferable that it is 70-100 mass%, and it is further more preferable that it is 80-100 mass%.
As an epoxy resin containing the structural unit represented by general formula (a1), the epoxy resin represented by the following general formula (a1-1) is mentioned, for example.

In general formula (a1-1), R ^a1 is the same as described above, and m ¹ represents an integer of ¹ to 20. The plurality of R ^a1 may be the same or different, but are preferably the same.

The bisphenol A novolac type epoxy resin can be represented by the following general formula (a2).

In the general formula (a2), ^{m 2} represents an integer of 1 to 10.

  In addition, (a) the epoxy resin may contain an epoxy resin that is liquid at room temperature (hereinafter sometimes abbreviated as “liquid epoxy resin”) from the viewpoint of improving the handleability when used as a film. Although it does not restrict | limit especially as a liquid epoxy resin, Bifunctional liquid epoxy resins, such as a bisphenol A type liquid epoxy resin, etc. are mentioned. When the (a) epoxy resin contains a liquid epoxy resin, the content is preferably 10 to 60% by mass with respect to the (a) epoxy resin from the viewpoint of improving the handleability of the resin composition for an interlayer insulating layer. More preferably, it is 10-50 mass%, More preferably, it is 10-40 mass%.

  (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 novolac epoxy resin having a biphenyl skeleton), “NC-7000-L” (trade name, naphthol novolac epoxy resin, manufactured by Nippon Kayaku Co., Ltd.), “jER828” (trade name, manufactured by Mitsubishi Chemical Corporation) Bisphenol A type epoxy resin), “jER157S70” (trade name, bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation), and the like.

(A) From the viewpoint of reflow heat resistance and the like, the epoxy equivalent of the epoxy resin is preferably 150 to 500 g / eq, more preferably 150 to 400 g / eq, and 170 to 350 g / eq. More preferably, it is 200-320 g / eq, and 170-230 g / eq may be sufficient, and 250-320 g / eq may be sufficient.
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 (2001). 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 (a) epoxy resin in the interlayer insulating layer resin composition is the solid content of the resin composition for interlayer insulating layer (here, (c) inorganic filler is excluded) from the viewpoint of reflow heat resistance and the like. ) It is preferable that it is 20-80 mass parts with respect to 100 mass parts, It is more preferable that it is 30-70 mass parts, It is further more preferable that it is 35-60 mass parts.
Here, the “solid content” in the present invention is a non-volatile content excluding volatile components such as an organic solvent, and a component that remains without being evaporated when the resin composition for an interlayer insulating layer is dried. Including those in liquid form, water tank form and wax form at room temperature. Here, in this specification, room temperature indicates 25 ° C.

[(B) Curing agent]
In the present invention, (b) the curing agent contains at least one selected from the group consisting of (b1) an active ester curing agent and (b2) a cyanate curing agent, or (b3) contains a triazine ring. A phenol novolac hardener.
(B1) to (b3) will be described below.

<(B1) Active ester curing agent>
The (b1) active ester curing agent is not particularly limited as long as it functions as a curing agent for the (a) epoxy resin and has an active ester. When (b1) an active ester curing agent is contained, the dielectric loss tangent tends to be reduced.
(B1) The active ester curing agent has a highly reactive ester group such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy ester compound, A compound having a curing action can be used.

(B1) The active ester curing agent is preferably a compound having two or more active ester groups in one molecule, and 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. In addition, the (b1) 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 (b2) the cyanate resin can be increased. If it is a compound which has a group ring, reflow heat resistance can be made high. In particular, from the viewpoint of heat resistance and the like, (b1) 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 reflow 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, tetrahydroxy More preferred are benzophenone, 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. There.
Examples of the thiol compound include benzenedithiol and triazinedithiol.

(B1) 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 (b1) active ester-based curing agents include compounds containing a dicyclopentadienyl diphenol structure, acetylated products of phenol novolac, benzoylated products of phenol novolac, and among these, dicyclopentadi Compounds containing an enyldiphenol structure are preferred. Specifically, as a compound containing a dicyclopentadienyl diphenol structure, “EXB9451” (active ester group equivalent: about 220 g / eq), “EXB9460”, “EXB9460S-65T”, “HPC-8000-65T” ( Active ester group equivalent: about 223 g / eq) (above, manufactured by DIC Corporation, trade name), “DC808” (manufactured by Mitsubishi Chemical Corporation, active ester group equivalent: about 149 g / eq) as phenol acetylated product, phenol Examples of benzoylated novolaks include “YLH1026” (manufactured by Mitsubishi Chemical Corporation, active ester group equivalent: about 200 g / eq).

  (B1) There is no restriction | limiting in particular in the manufacturing method of an active ester type hardening | curing agent, It can manufacture by a well-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.

((B2) cyanate curing agent)
As the (b2) cyanate-based curing agent, a known cyanate resin can be used. As the cyanate resin, for example, a cyanate resin having two or more cyanate groups in one molecule is preferably exemplified.
(B2) Specific examples of the cyanate curing agent include 2,2-bis (4-cyanatophenyl) propane [bisphenol A type cyanate resin], bis (4-cyanatophenyl) ethane [bisphenol E type cyanate. Resin], bis (3,5-dimethyl-4-cyanatophenyl) methane [tetramethylbisphenol F type cyanate resin], 2,2-bis (4-cyanatophenyl) -1,1,1,3,3 Bisphenol type cyanate resin such as 1,3-hexafluoropropane [hexafluorobisphenol A type cyanate resin]; dicyclopentadiene type cyanate resin such as cyanate ester compound of phenol-added dicyclopentadiene polymer; phenol novolac type cyanate ester compound, cresol Novolac Cyanate S Novolak-type cyanate resins such as copper compounds; α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene; prepolymers of these cyanate resins (hereinafter also referred to as “cyanate prepolymer”), and the like . You may use these individually or in mixture of 2 or more types.
Among these, from the viewpoint of reflow heat resistance and the like, a cyanate resin represented by the following general formula (b2-I), a cyanate resin represented by the following general formula (b2-IV), and these prepolymers are preferable. A cyanate resin represented by the general formula (b2-I) and a prepolymer thereof are more preferable.

In general formula (b2-I), R ^b1 represents an alkylene group having 1 to 3 carbon atoms which may be substituted with a halogen atom, a sulfur atom, the following general formula (b2-II) or the following general formula (b2-III). ) Is a divalent group represented by: R ^b2 and R ^b3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A plurality of R ^b2 or R ^b3 may be the same or different from each other, but are preferably the same.

In the general formula (b2-II), R ^b4 represents an alkylene group having 1 to 3 carbon atoms. The plurality of ^Rb4s may be the same or different, but are preferably the same.

In the general formula (b2-IV), R ^b5 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 ^b5 may be the same or different, but are preferably the same.

In the general formula (b2-I), the alkylene group having 1 to 3 carbon atoms represented by R ^b1 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, from the viewpoint of reflow heat resistance and the like, 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 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 (b2-II), the alkylene group having 1 to 3 carbon atoms represented by R ^b4 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 ^b1 , from the viewpoint of reflow heat resistance and the like, 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 preferred.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^b2 or R ^b3 in the general formula (b2-I) include a methyl group, an ethyl group, a propyl group, and a butyl group.

^Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^b5 in the general formula (b2-IV) 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.
In general formula (b2-IV), n represents an integer of 1 or more, and is preferably 1 to 7, more preferably 1 to 4, from the viewpoint of reflow heat resistance and the like.

The cyanate prepolymer refers to a polymer in which a cyanate resin forms a triazine ring by a cyclization reaction, and examples thereof include 3, 5, 7, 9, and 11 mer of cyanate ester compounds. In this cyanate prepolymer, the conversion rate of the cyanate group is not particularly limited, but is preferably 20 to 70% by mass, and preferably 30 to 65% by mass from the viewpoint of obtaining good solubility in an organic solvent. More preferred.
Examples of the cyanate prepolymer include a prepolymer of a cyanate resin represented by the general formula (b2-I), a prepolymer of a cyanate resin represented by the general formula (b2-IV), and the like. Among these, from the viewpoint of reflow heat resistance and the like, a prepolymer of a dicyanate compound having two cyanato groups in one molecule is preferable, and a prepolymer of a cyanate resin represented by the general formula (b2-I) is used. More preferably, it is a polymer, and is a prepolymer (see formula (b2-V) below) in which at least a part of 2,2-bis (4-cyanatophenyl) propane is triazine to form a trimer. More preferably.

The weight average molecular weight (Mw) of the cyanate prepolymer is not particularly limited, but is preferably 500 to 4,500 and more preferably 600 to 4,000 from the viewpoints of solubility in an organic solvent and workability. Preferably, it is 1,000 to 4,000, more preferably 1,500 to 4,000. If the weight average molecular weight (Mw) of the cyanate prepolymer is 500 or more, crystallization of the cyanate prepolymer tends to be suppressed and the solubility in an organic solvent tends to be good, and if it is 4,500 or less, The increase in viscosity is suppressed and the workability tends to be excellent.
In the present invention, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a standard polystyrene calibration curve. It was measured according to the method described in 1.

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 the monofunctional phenol compound include alkyl group-substituted phenol compounds such as p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol; p- (α-cumyl) phenol, mono- And phenol compounds represented by the following general formula (b2-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 (b2-VI), R ^b6 and R ^b7 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 ^b6 or R ^b7 may be the same or different, but are preferably the same.

  The amount of the monofunctional phenol compound used is such that the equivalent ratio (hydroxyl group / cyanato group) between the phenolic hydroxyl group of the monofunctional phenol compound and the cyanate group of the cyanate resin is 0.01 to 0.30. The amount is preferably 0.01 to 0.20, more preferably 0.01 to 0.15. When the amount of the monofunctional phenol compound is within the above range, in particular, there is a tendency to obtain a sufficiently low dielectric loss tangent in a high frequency band, and in addition, 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.

A commercially available product may be used as the cyanate resin. Examples of commercially available 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.

((B3) Phenol novolak curing agent containing a triazine ring)
(B3) As a phenol novolak type | system | group hardening | curing agent containing a triazine ring, what contains a triazine ring among the novolak-type phenol resins used as a hardening | curing agent of an epoxy resin can be used. The novolak type phenol resin containing a triazine ring is obtained by randomly bonding an aminotriazine ring structure and a phenol structure via a methylene group. As a phenol novolak type | system | group hardening | curing agent containing a triazine ring, the phenol novolak resin containing a triazine ring, the cresol novolak resin containing a triazine ring, etc. are preferable.
The novolak-type phenol resin containing a triazine ring can be produced, for example, by utilizing the production method described in JP-A-2002-226556. That is, a phenol compound, an aminotriazine compound, and an aldehyde compound can be produced by a cocondensation reaction in the presence of a weak alkaline catalyst such as an alkylamine or in the absence of a catalyst in the vicinity of neutrality.

Examples of the phenol compound used as a raw material include phenol, ortho-cresol, meta-cresol, para-cresol, xylenol, bisphenol compound, ortho-substituted phenol compound having a hydrocarbon group having 3 or more carbon atoms, preferably 3 to 10 carbon atoms in the ortho position. And para-substituted phenol compounds 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. It is done.
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- Examples include dodecylphenol and 4-octadecylphenol.

Examples of the aminotriazine compound used as a raw material include melamine, benzoguanamine, and acetoguanamine.
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.
Moreover, the nitrogen atom content in the phenol novolak-type curing agent containing a (b3) triazine ring is preferably 8 to 30%, more preferably 8 to 20%.

  (B3) As a phenol novolak type | system | group hardening | curing agent containing a triazine ring, a commercial item can be used, "PAPS-PN2" (Asahi Organic Materials Co., Ltd. make, brand name), "PAPS-PN3" (Asahi Organic Material Industries Co., Ltd., trade name), “Phenolite LA-1356” (DIC Corporation, trade name), “Phenolite LA-7054” (Triazine-containing phenol novolac resin, DIC Corporation, trade name) , “Phenolite LA-3018” (triazine-containing cresol novolac resin, manufactured by DIC Corporation, trade name), and the like.

The (b) curing agent of the resin composition for an interlayer insulating layer of the present invention is an epoxy resin curing agent other than the curing agents (b1) to (b3) (hereinafter, simply “ Also referred to as “epoxy resin curing agent”.
Examples of the epoxy resin curing agent include a phenol resin not containing a triazine ring, a phosphorus-containing phenol compound, an acid anhydride compound, an amine compound, and a hydragit compound.
Examples of the phenol resin not containing a triazine ring include novolak type phenol resins and resol type phenol resins. The phosphorus-containing phenol compound is a compound having two or more phenolic hydroxyl groups and containing a phosphorus atom, and 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phos. Faphenanthrene-10-oxide [HCA-HQ or HCA-HQ-HS (trade name, manufactured by Sanko Co., Ltd.)] and the like. Examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. Examples of the amine compound include dicyandiamide, diaminodiphenylmethane, and guanylurea.
Among these epoxy resin curing agents, a phenol resin not containing a triazine ring and a phosphorus-containing phenol compound are preferable from the viewpoint of improving reliability, and a phosphorus-containing phenol compound is more preferable from the viewpoint of flame retardancy.
In the present invention, those having other functions in addition to the function as a curing agent are classified as “curing agents” with priority given to having the function as a curing agent. For example, the phosphorus-containing phenol compound has a function as a curing agent and also has a function as a flame retardant, but is classified as a curing agent.

  In particular, from the viewpoint of dielectric properties, (b) the curing agent preferably includes (b1) an active ester curing agent, and (b1) an active ester curing agent and (b2) a cyanate curing agent or (b3) It is also preferable to contain a phenol novolac curing agent containing a triazine ring.

There are no particular restrictions on the content of each of (b1) an active ester-based curing agent, (b2) a cyanate-based curing agent, and (b3) a phenol novolac-based curing agent containing a triazine ring in (b) the curing agent. When the component (b1) is combined with the component (b2) or the component (b3), the component (b1) is used with respect to the total amount of the components (b1) to (b3) to be used from the viewpoint of dielectric properties. Is preferably 40 to 70% by mass, and more preferably 50 to 65% by mass.
(B) The mass ratio of the total amount of the components (b1) to (b3) in the curing agent is preferably 20% by mass or more, more preferably 40% by mass or more, and more preferably 40% by mass or more, from the viewpoints of reflow heat resistance and dielectric properties. Preferably it is 60 mass% or more, Most preferably, it is 80 mass% or more. There is no restriction | limiting in particular in an upper limit, 100 mass% may be sufficient.

  In the resin composition for an interlayer insulating layer, the content ratio of (a) the epoxy resin and (b) the curing agent is the above (b) with respect to the total number of epoxy groups in the (a) epoxy resin from the viewpoint of reflow heat resistance and the like. ) The ratio of the total number of functional groups of the curing agent [(b) the total number of functional groups of the curing agent / (a) the total number of epoxy groups of the epoxy resin] may be adjusted to be 0.2-2. preferable. When the ratio is 0.2 or more, the amount of unreacted epoxy groups in the obtained interlayer insulating layer tends to be reduced, and when it is 2 or less, the blending amount of (b) the curing agent becomes too large. Therefore, there is a tendency that an increase in the curing temperature can be suppressed. From the same viewpoint, the ratio is more preferably 0.4 to 1.5.

[(C) Inorganic filler]
The resin composition for interlayer insulation layers further contains (c) an inorganic filler. (C) The inorganic filler can prevent the resin from scattering and adjust the shape of the laser processing when laser processing the interlayer insulating layer formed by thermosetting the resin composition for the interlayer insulating layer. It is important from the viewpoint of Further, when the surface of the interlayer insulating layer is roughened with an oxidizing agent, it is important from the viewpoint of forming an appropriate roughened surface and enabling formation of a conductor layer having excellent adhesive strength by plating. It is preferable to select from.

  (C) As an 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, particularly spherical silica and fused silica are preferred from the viewpoints of thermal expansion coefficient, varnish handling properties and insulation reliability. Inorganic fillers may be used alone or in admixture of two or more.

(C) The inorganic filler preferably has a small particle size from the viewpoint of forming fine wiring. From the same viewpoint, (c) the inorganic filler is preferably one having a specific surface area of at ^3m 2 / g or more, may be 3~200m ² / g, it may be 3~130m ² / g , may be 3 to 50 m ² / g, it may be 3 to 20 m 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.
In addition, the volume average particle diameter of the inorganic filler (c) is preferably 0.01 to 5 μm, more preferably 0.1 to 2 μm, from the viewpoint of obtaining good circuit board embedding properties and insulation reliability. 0.2-1 micrometer is further more preferable. 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.
(C) As an inorganic filler, you may use a commercial item, "AEROSIL (Aerosil) (registered trademark) R972" which is fumed silica (Nippon Aerosil Co., Ltd., brand 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).

(C) As an inorganic filler, from the viewpoint of reflow moisture resistance, an inorganic filler surface-treated with a surface treatment agent may be used. Examples of the surface treatment agent include a coupling agent. Examples of the coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, and haloalkylsilanes. Coupling agent, siloxane coupling agent, hydrosilane coupling agent, silazane coupling agent, alkoxysilane coupling agent, chlorosilane coupling agent, (meth) acrylsilane coupling agent, aminosilane coupling Agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, and the like. Among these, aminosilane coupling agents are preferred from the viewpoints of reflow heat resistance, high filling of inorganic fillers, low thermal expansion, dielectric properties, desmear resistance, and smear removability. That is, it is preferable that (c) the inorganic filler contains an inorganic filler surface-treated with an aminosilane coupling agent.
Commercially available products may be used as the surface-treated inorganic filler, “SO-C2” (trade name, manufactured by Admatechs Co., Ltd.), which is a silica filler surface-treated with an aminosilane coupling agent, and phenylsilane cup. “YC100C” (trade name) manufactured by Admatex Co., Ltd., a silica filler surface-treated with a ring agent, and “Sciquas series” (manufactured by Sakai Chemical Industry Co., Ltd.), a silica filler surface-treated with an epoxysilane coupling agent. , Trade name, 0.1 μm grade) and the like.

  In the resin composition for an interlayer insulating layer, the content of the inorganic filler (c) is the solid content of the resin composition for an interlayer insulating layer from the viewpoint of the laser processability of the obtained interlayer insulating layer and the adhesive strength with the conductor layer. It is preferably 50 to 90% by mass, more preferably 50 to 80% by mass, and further preferably 60 to 80% by mass with respect to the minute (including (c) the inorganic filler itself). . When it is 50% by mass or more with respect to the solid content of the resin composition for an interlayer insulating layer, good laser processability tends to be obtained, and when it is 90% by mass or less, a conductor layer formed by a plating method is used. The adhesive strength tends to be excellent.

[(D) Resin having a polysiloxane skeleton]
The resin composition for interlayer insulation layers further contains (d) a resin having a polysiloxane skeleton. (D) Resin having a polysiloxane skeleton suppresses repellency efficiently, so the film thickness can be easily adjusted. In particular, when the (b1) active ester curing agent is used, repellency is likely to occur, and the (c) inorganic filler contains silica that has been surface-treated (particularly surface-treated with an aminosilane coupling agent). In this case, repelling is likely to occur. In order to avoid such repellency, if you try to avoid the use of the causative curing agent and the use of the surface-treated inorganic filler itself, reflow heat resistance, high inorganic filler filling, low heat Although there were problems that various properties such as expansion coefficient, dielectric properties, desmear resistance and smear removability deteriorated, it was difficult to achieve both, but (d) resin having a polysiloxane skeleton reduced these disadvantages. The effect of suppressing repelling can be obtained.

More precisely, the polysiloxane skeleton is a polyorganosiloxane skeleton, and the skeleton is represented by a unit represented by monofunctional R ₃ SiO _1/2 and a bifunctional R ₂ SiO _2/2. And polyorganosiloxanes formed with units represented by trifunctional RSiO _3/2 and units represented by tetrafunctional SiO _4/2 . Among these, polyorganosiloxane formed with a unit represented by difunctional R ₂ SiO _2/2 is preferable.
As said organic group (R) of polyorganosiloxane, it can select from hydrocarbon groups, such as an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group, for example. Usually, it is a C1-C4 alkyl group and a C6-C12 aryl group, a methyl group and a phenyl group are preferable and a methyl group is more preferable. The number of repeating siloxane units (degree of polymerization) is preferably 2 to 3,000, more preferably 3 to 2,000, and still more preferably 5 to 1,000.

  (D) Examples of the resin having a polysiloxane skeleton include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, poly Examples include ether-modified polymethylalkylsiloxane. Among these, polyether-modified polydimethylsiloxane and polyester-modified polydimethylsiloxane are preferable from the viewpoint of suppressing repellency.

(D) As specific examples of the resin having a polysiloxane skeleton that can be used as the resin having a polysiloxane skeleton, the following commercially available products can be used. For example, BYK-354, BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-313, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-342, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-370, BYK-378, BYK-3455 (above, Big Chemie Japan Co., Ltd.), Tegorad-2100, Tegorad-2200, Tegorad-2250, Tegorad-2500, Tegorad-2700 (above, Tegochemy Co., Ltd.), Surflon S-611 (AGC Seimi Chemical Co., Ltd.), Tore Silicone DC3PA Torre Silicone DC7PA, Torre Silicone SH11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH-190, Torree Silicone SH-193, Torree Silicone SZ-6032, Torree Silicone SF-8428, Torree Silicone DC-57, Torre Silicone DC-190 (above, manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, Momentive Performance・ Materials Japan Co., Ltd.).
The above-mentioned resins having a polysiloxane skeleton may be used alone or in combination of two or more.

The content of the resin having a (d) polysiloxane skeleton in the interlayer insulating layer resin composition is 0 with respect to the solid content of the interlayer insulating layer resin composition (including the inorganic filler (c)). 0.01 to 1% by mass. If the content is 0.01% by mass or more based on the solid content of the resin composition for an interlayer insulating layer (including the inorganic filler (c)), an effect of suppressing repellency can be obtained. From this viewpoint, the content of the resin (d) having a polysiloxane skeleton is preferably 0.03% by mass with respect to the solid content of the resin composition for an interlayer insulating layer (including the inorganic filler (c)). As mentioned above, More preferably, it is 0.04 mass% or more.
On the other hand, when the amount exceeds 1 part by mass, the surface roughness after desmear treatment, which will be described later, is increased and an unroughened portion is generated. There was found. In particular, in the case of producing a multilayer printed wiring board using a multilayer resin film that also contains an adhesion auxiliary layer, the exact reason is unknown, but (d) the polysiloxane skeleton in the resin composition for interlayer insulating layers It was found that even if the content of the resin having a change was changed and the content of the resin having a polysiloxane skeleton in the adhesion auxiliary layer was not changed, an unroughened portion was generated on the surface of the adhesion auxiliary layer.
From the viewpoint of solving such problems, the content of the resin (d) having a polysiloxane skeleton is preferably relative to the solid content of the resin composition for an interlayer insulating layer (including the inorganic filler (c)). Is 0.7% by mass or less, more preferably 0.5% by mass or less, further preferably 0.40% by mass or less, and particularly preferably 0.30% by mass or less.
From the above, the content of the resin having the (d) polysiloxane skeleton is preferably 0.01 to 0.00 relative to the solid content of the resin composition for an interlayer insulating layer (including the inorganic filler (c)). 7 mass%, more preferably 0.03-0.7 mass%, still more preferably 0.03-0.5 mass%, particularly preferably 0.03-0.40 mass%, most preferably 0.03- 0.30.

[(E) Phenoxy resin]
The resin composition for an interlayer insulating layer of the present invention preferably further contains (e) a phenoxy resin.
Here, the “phenoxy resin” is a general term for polymers whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether. In the present specification, the weight average molecular weight is 10,000. It refers to the above. When the polymer whose main chain is a polyaddition structure of aromatic diol and aromatic diglycidyl ether has an epoxy group, those having a weight average molecular weight of 10,000 or more are classified as (e) phenoxy resin, Those having an average molecular weight of less than 10,000 are classified as (a) epoxy resin.

(E) It is preferable that a phenoxy resin contains an alicyclic structure from a viewpoint of the handleability of the film for interlayer insulation layers. Here, the “alicyclic structure” means “an organic compound having a structure in which carbon atoms are bonded cyclically, excluding an aromatic compound”. Among these, at least one selected from cyclic saturated hydrocarbons (cycloalkanes) and cyclic unsaturated hydrocarbons having one double bond in the ring (cycloalkene) is preferable.
(E) Examples of the phenoxy resin include a phenoxy resin containing a cyclohexane structure, a phenoxy resin containing a trimethylcyclohexane structure, and a phenoxy resin containing a terpene structure. Among these, a phenoxy resin containing one or more selected from a terpene structure and a trimethylcyclohexane structure is preferable, and a phenoxy resin containing a trimethylcyclohexane structure is more preferable from the viewpoint of improving the handleability when a film is formed.
As a phenoxy resin containing a trimethylcyclohexane structure, a phenoxy resin using bisphenol TMC (bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane) as a raw material disclosed in JP-A-2006-176658 is disclosed. Etc.
As a phenoxy resin containing a terpene structure, for example, in the phenoxy resin disclosed in Japanese Patent Application Laid-Open No. 2006-176658, bis (4-hydroxyphenyl) -3,3,5- Examples thereof include phenoxy resins synthesized using terpene diphenol instead of trimethylcyclohexane.
(E) A phenoxy resin may be used individually by 1 type, and may use 2 or more types together.

(E) The weight average molecular weight of the phenoxy resin is preferably 10,000 to 60,000, more preferably 12,000 to 50,000, still more preferably 15,000 to 45,000, and 17,000 to 40,000. Is particularly preferable, and 20,000 to 37,000 is very preferable. (E) When the weight average molecular weight of the phenoxy resin is equal to or higher than the lower limit, an excellent peel strength with the conductor layer tends to be obtained, and when the weight average molecular weight is equal to or lower than the upper limit, an increase in roughness and a coefficient of thermal expansion are obtained. An increase can be prevented.
A weight average molecular weight is the value measured by the gel permeation chromatography (GPC) method (polystyrene conversion), and can be measured by the method as described in an Example.

  (E) As a method for producing a phenoxy resin, for example, a bisphenol compound containing a trimethylcyclohexane structure or a bisphenol compound containing a terpene structure and a bifunctional epoxy resin are used as raw materials in accordance with a known phenoxy resin production method. It can manufacture by making it react in the range from which the equivalence ratio (phenolic hydroxyl group / epoxy group) of a functional hydroxyl group and an epoxy group becomes 1 / 0.9-1 / 1.1, for example.

  (E) A commercially available product can be used as the phenoxy resin. The commercially available (e) phenoxy resin is derived from a biphenyl type epoxy resin and a bisphenol compound having a trimethylcyclohexane structure (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane). “YX7200B35” (trade name, manufactured by Mitsubishi Chemical Corporation) containing a skeleton is preferable.

  When the resin composition for interlayer insulation layers contains (e) phenoxy resin, the content thereof is 100 parts by mass of the solid content of the resin composition for interlayer insulation layers (here, (c) excludes inorganic filler). On the other hand, 0.2-30 mass parts is preferable, 1-20 mass parts is more preferable, and 5-20 mass parts is further more preferable. (E) When the content of the phenoxy resin is 0.2 parts by mass or more, the flexibility and the handleability tend to be excellent, and the peel strength of the conductor layer tends to be excellent. In addition to excellent stability and fluidity, an appropriate roughness tends to be obtained.

[(F) Curing accelerator]
The resin composition for interlayer insulation layers may contain the (f) hardening accelerator from a viewpoint which enables hardening for a short time at low temperature.
(F) As a hardening accelerator, a metal type hardening accelerator, an organic type hardening accelerator, etc. are mentioned.

(Metal curing accelerator)
As the metal curing accelerator, for example, an organometallic curing accelerator can be used. The organometallic curing accelerator has (b2) a self-polymerization reaction promoting action of the cyanate curing agent and (a) a reaction promoting action of the epoxy resin and (b) curing agent.
Examples of the organometallic curing accelerator include transition metals, organometallic salts of group 12 metals, organometallic complexes, and the like. Examples of the metal include copper, cobalt, manganese, iron, nickel, zinc, tin and the like.
Examples of the organic metal salt include carboxylates, and specific examples thereof include naphthenates such as cobalt naphthenate and zinc naphthenate, 2-ethylhexanoate cobalt and 2-ethylhexanoate zinc and the like. Examples include hexanoate, zinc octylate, tin octylate, tin stearate, and zinc stearate.
Examples of the organometallic complex include chelate complexes such as acetylacetone complex, and specific examples thereof include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; copper (II) acetylacetonate Organic copper complexes such as zinc (II) acetylacetonate; organic iron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; manganese (II) acetyl And organic manganese complexes such as acetonate. Among these, from the viewpoint of curability and solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, iron (III) acetylacetonate, zinc naphthenate, naphthene Cobalt acid is preferred, and cobalt naphthenate is more preferred. You may use these individually or in mixture of 2 or more types.

  When the resin composition for interlayer insulation layers contains a metal curing accelerator, the content is preferably 1 to 500 ppm by mass with respect to (b2) the cyanate curing agent from the viewpoint of reactivity and storage stability. 10-500 mass ppm is more preferable, 50-400 mass ppm is further more preferable, and 150-300 mass ppm is especially preferable. You may mix | blend a metal type hardening accelerator at once or in multiple steps.

(Organic curing accelerator)
Examples of the organic curing accelerator (not including the organometallic curing accelerator) include organic phosphorus compounds, imidazole compounds, and amine compounds. You may use these individually or in mixture of 2 or more types. From the viewpoint of removing smear in the via hole, at least one selected from the group consisting of an organic phosphorus compound, an imidazole compound and an amine compound is preferable, and at least one selected from the group consisting of an organic phosphorus compound and an amine compound Is more preferable. The organic curing accelerator may be blended at one time or divided into a plurality of times.

Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetraphenyl Examples thereof include phosphonium tetraphenylborate. Among these, triphenylphosphine is preferable.
In addition, the phosphorus compound may be 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, as shown in JP2011-179008A, An addition reaction product of tris (p-methylphenyl) phosphine and 1,4-benzoquinone is preferable.

Examples of the imidazole compound include 2-phenyl-4-methylimidazole and 1-cyanoethyl-2-phenylimidazolium trimellitate.
Examples of amine compounds include amine compounds such as secondary amines and tertiary amines; and quaternary ammonium salts. Specific examples include amine adduct compounds, 1,8-diazabicyclo [5.4.0] undecene 7, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and the like. It is done. Among these, a tertiary amine is preferable and 4-dimethylaminopyridine is more preferable.

  When the resin composition for interlayer insulation layers contains an organic hardening accelerator, the content is 0.01-5 with respect to 100 mass parts of (a) epoxy resin from a viewpoint of reactivity and storage stability. Mass parts are preferred, 0.01-3 parts by mass are more preferred, and 0.01-2 parts by mass are even more preferred.

<Other ingredients>
The resin composition for interlayer insulation layers 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, flame retardants, and the like.

(Other resin components)
Examples of other resin components include a polymer of a bismaleimide compound and a diamine compound, a bismaleimide compound, a bisallyl nazide resin, and a benzoxazine compound.

(Additive)
Examples of the additives include antioxidants; thickeners such as olben and benton; adhesion imparting agents such as imidazole, thiazole, triazole and silane coupling agents; rubber particles; colorants and the like.

(Flame retardants)
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.

  The resin composition for interlayer insulation layers can be produced by mixing the components (a) to (d) and, if necessary, the components (e) to (f) and other components. As a mixing method, a known method can be applied. For example, the mixing may 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 is formed using the thermosetting resin composition of the present invention (resin composition for interlayer insulation layers).
In addition, the resin film for interlayer insulation layers may generally be called an interlayer insulation film.

<Thickness of resin film for interlayer insulation layer>
The thickness of the interlayer insulating layer resin film can be determined by the thickness of the conductor layer formed on the printed wiring board. Since the thickness of the conductor layer is usually 5 to 70 μm, the thickness of the resin film for the interlayer insulating layer is preferably 10 to 100 μm. From the viewpoint of enabling the multilayer printed wiring board to be thinned, 15 to 15 μm is preferable. 80 micrometers is more preferable and 20-50 micrometers is still more preferable.

<Support>
The resin film for an interlayer insulating layer of the present invention may be formed on a support.
Examples of the support include organic resin films, metal foils, release papers, and the like. In the present invention, as described later, from the viewpoint of curing the multilayer resin film with the support attached, the support is preferably an organic resin film subjected to a release treatment.
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, the thickness of copper foil can be 2-36 micrometers, for example. When using thin copper foil, you may use copper foil with a carrier from a viewpoint of improving workability | operativity.
As one embodiment of the present invention, a multilayer resin film having the interlayer insulating layer resin film and the organic resin film can be cited. As will be described later, the multilayer resin film may contain a layer made of a resin film for an interlayer insulating layer (a resin composition layer for an interlayer insulating layer) and an adhesion auxiliary layer. The details of the adhesion auxiliary layer will be described later.
As described above, the present invention also provides a multilayer resin film having the interlayer insulating layer resin film or the multilayer resin film having the adhesion auxiliary layer and the organic resin film subjected to the release treatment.

These supports and a protective film to be described later may be subjected to a surface treatment such as a mold release treatment, a plasma treatment, or a corona treatment. Examples of the release treatment include a release treatment using a silicone resin release agent, an alkyd resin release agent, a fluororesin release agent, or the like.
The thickness of the support is preferably from 10 to 120 μm, more preferably from 15 to 80 μm, and even more preferably from 25 to 50 μm, from the viewpoints of handleability and economy.
When producing a multilayer printed wiring board, the support is usually finally peeled off or removed.

<Protective film>
A protective film may be arranged on the surface opposite to the support of the resin film for an interlayer insulating layer of the present invention. The protective film is provided on the surface opposite to the surface on which the support for the resin film for the interlayer insulating layer is provided, and prevents the adhesion and scratches of foreign matters to the resin film for the interlayer insulating layer. Used for purposes. The protective film is peeled off before the interlayer insulating layer resin film is laminated on a circuit board or the like by laminating or hot pressing.
As the protective film, the same material as the support can be used. For example, a protective film having a thickness of 1 to 40 μm can be used.

<Method for producing resin film for interlayer insulating layer>
The resin film for interlayer insulation layers of the present invention can be produced, for example, by applying a resin composition for interlayer insulation layers on a support and then drying. At that time, the resin composition for an interlayer insulating layer is preferably dissolved and / or dispersed in an organic solvent to form a varnish.

(Organic solvent)
Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), methyl isobutyl ketone, and cyclohexanone; acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Examples include ester solvents; 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. 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.

  As a method of coating the resin composition for an interlayer insulating layer, a method of coating 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. it can. What is necessary is just to select a coating apparatus suitably according to the target film thickness.

As drying conditions after coating the resin composition for interlayer insulation layers, it is preferable to dry so that the content of the organic solvent in the obtained resin film for interlayer insulation layers is 10% by mass or less. It is more preferable to dry so that it may become mass% or less.
Although drying conditions change also with the quantity and kind of organic solvent in a varnish, if it is a varnish containing 20-80 mass% organic solvent, what is necessary is just to dry for 1 to 10 minutes at 50-150 degreeC.

[Multilayer Resin Film Containing Interlayer Insulating Layer Resin Composition Layer and Adhesion Auxiliary Layer]
Next, as one aspect of the multilayer resin film of the present invention, a multilayer resin film containing a resin composition layer for an interlayer insulating layer and an adhesion auxiliary layer will be described.
The multilayer resin film is a multilayer resin film containing an organic resin film, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer made of the resin film for an interlayer insulating layer of the present invention in this order.

<Resin composition layer for interlayer insulation layer>
The resin composition layer for interlayer insulation layers is a layer which consists of the resin film for interlayer insulation layers of this invention.
The resin composition layer for an interlayer insulating layer is a layer provided between a circuit board and an adhesion auxiliary layer in the case of producing a multilayer printed wiring board using a multilayer resin film having an adhesion auxiliary layer. The insulating layer obtained by curing the resin composition layer for layers serves to insulate the circuit patterns that have been multilayered, for example, in a multilayer printed wiring board. In addition, when a through hole, a via hole or the like is present in the circuit board, the resin composition layer for an interlayer insulating layer also flows in the circuit board and fills the inside of the hole.

  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. Since the thickness of the conductor layer is usually 5 to 70 μm, the thickness of the resin composition layer for the interlayer insulating layer is preferably 10 to 100 μm, from the viewpoint of enabling the multilayer printed wiring board to be thinned. 15-80 micrometers is more preferable and 20-50 micrometers is further more preferable.

<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 10 μm and more preferably 2 to 8 μm from the viewpoint of obtaining an interlayer insulating layer having high adhesion to the conductor layer.
An adhesion auxiliary layer can be formed using the resin composition for adhesion auxiliary layers.

(Resin composition for adhesion auxiliary layer)
From the viewpoint of obtaining an interlayer insulating layer having a smooth surface and high adhesion to a conductor layer, the resin composition for an adhesion auxiliary layer is (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. It is preferable to contain. About (A) epoxy resin, (B) curing agent, and (C) inorganic filler, (a) epoxy resin, (b) curing agent, and (c) inorganic filler in the resin composition for interlayer insulation layers, respectively. It will be explained in the same way as the explanation.

When the resin composition for an adhesion auxiliary layer contains (A) an epoxy resin, the content is 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. 20-80 mass parts is preferable with respect to 100 mass parts of solid content ((C) inorganic filler is also included) of a resin composition, 30-70 mass parts is more preferable, and 40-60 mass parts is further more preferable.
When the resin composition for an adhesion auxiliary layer contains (B) a curing agent, the content is 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. 5-50 mass parts is preferable with respect to 100 mass parts of solid content ((C) inorganic filler is also included) of a resin composition, 10-40 mass parts is more preferable, and 20-35 mass parts is further more preferable.
The mass ratio [(A) / (B)] of (A) epoxy resin and (B) curing agent in the resin composition for the adhesion auxiliary layer is an interlayer insulating layer having high adhesion to the conductor layer. From the viewpoint of obtaining, 0.5 to 5 is preferable, 1 to 3 is more preferable, and 1.2 to 2.5 is more preferable.

  When the resin composition for an adhesion auxiliary layer contains (C) an inorganic filler, the content is an adhesion auxiliary layer from the viewpoint of obtaining an interlayer insulating layer having a smooth surface and high adhesion to the conductor layer. 3 to 40 parts by weight, preferably 5 to 30 parts by weight, and more preferably 7 to 20 parts by weight with respect to 100 parts by weight of the solid content of the resin composition (including the inorganic filler (C)). . (C) When the content of the inorganic filler is 3 parts by mass or more, it is possible to prevent resin scattering during laser processing and to arrange the laser processing shape of the interlayer insulating layer, and when it is 40 parts by mass or less. High plating peel strength can be obtained.

  The resin composition for an adhesion auxiliary layer may further contain at least one selected from the group consisting of (D) a resin having a polysiloxane skeleton, (E) a phenoxy resin, and (F) a curing accelerator. Furthermore, you may contain the other resin component, additive, a flame retardant, etc. Explained in the same manner as (d) a resin having a polysiloxane skeleton, (e) a phenoxy resin and (f) a curing accelerator, and other resin components, additives and flame retardants in the resin composition for an interlayer insulating layer. Is done.

  When the resin composition for an adhesion auxiliary layer contains (D) a resin having a polysiloxane skeleton, the content is preferably 0.01 to 1% by mass relative to the solid content of the resin composition for the adhesion auxiliary layer. 0.05 to 1 mass% is more preferable, and 0.05 to 0.5 mass% is more preferable.

  In particular, as the (F) curing accelerator, an organic phosphorus compound is preferable, and triphenylphosphine is more preferable. When the resin composition for an adhesion auxiliary layer contains (F) a curing accelerator, the content varies depending on the type of (F) curing accelerator. For example, (F) an organophosphorus compound is used as the curing accelerator. When it contains, (A) 0.001-2 mass part is preferable with respect to 100 mass parts of solid content of an epoxy resin, 0.002-1 mass part is more preferable, 0.01-1 mass part is further more preferable. .

In particular, the other resin component preferably contains at least one selected from the group consisting of a polyamide resin, a polyimide resin, and a polybenzoxazole resin. Among these, it is preferable to contain a polyamide resin from the viewpoint of obtaining an interlayer insulating layer having a small surface roughness and excellent adhesion strength with a conductor layer formed by a plating method.
The polyamide resin has a small surface roughness and a functional group that reacts with a thermosetting resin (for example, an epoxy group of an epoxy resin) from the viewpoint of obtaining an interlayer insulating layer having excellent adhesion strength with a conductor layer formed by plating. Those containing (phenolic hydroxyl group, amino group, etc.) are preferred, and those containing phenolic hydroxyl groups are more preferred. From the same viewpoint, the polyamide resin preferably further contains a polybutadiene skeleton.
Such a polyamide resin is represented by the structural unit represented by the following general formula (7-1), the structural unit represented by the following general formula (7-2), and the following general formula (7-3). A phenolic hydroxyl group-containing polybutadiene-modified polyamide resin containing a structural unit is preferred.

In general formulas (7-1) to (7-3), a, b, c, x, y, and z are average polymerization degrees, respectively, a is 2 to 10, b is 0 to 3, and c is An integer of 3 to 30 is shown, y + z = 2 to 300 ((y + z) / x) with respect to x = 1, and z ≧ 20 (z / y) with respect to y = 1.
R ^K1 , R ^K2 and R ^K3 are each independently a divalent group derived from an aromatic diamine or an aliphatic diamine, and R ^K4 is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or a carboxy group at both ends. It is a divalent group derived from an oligomer having

Aromatic diamines used in the production of phenolic hydroxyl group-containing polybutadiene-modified polyamide resins include diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxy. Biphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenediamine, methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), methylenebis ( Diethoxyaniline), isopropylidenedianiline, Aminobenzophenone, diamino dimethyl benzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, diaminodiphenyl sulfoxide, diaminofluorene and the like.
Aliphatic diamines used in the production of phenolic hydroxyl group-containing polybutadiene-modified polyamide resins include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminodiethylamine, diaminopropylamine, cyclopentanediamine, and cyclohexanediamine. , 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 in the production of the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid.
Examples of the dicarboxylic acid not containing a phenolic hydroxyl group used in the production of a phenolic hydroxyl group-containing polybutadiene-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.

Commercially available products may be used as the phenolic hydroxyl group-containing polybutadiene-modified polyamide resin. Examples of commercially available products include polyamide resins “BPAM-01” and “BPAM-155” manufactured by Nippon Kayaku Co., Ltd.
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 adhesive strength with a conductor layer formed by plating, and “BPAM-155” is preferable. Is more preferable. “BPAM-155” is a rubber-modified polyamide resin having an amino group at the terminal and has reactivity with an epoxy group, and therefore an interlayer insulating layer obtained from a thermosetting resin composition containing “BPAM-155” Is more excellent in the adhesive strength with a conductor layer formed by plating, and the surface roughness tends to be small.

The number average molecular weight of the polyamide resin is preferably 20,000 to 30,000, more preferably 22,000 to 29,000, from the viewpoints of solubility in a solvent and film thickness retention of the adhesion assist layer after lamination. 24,000 to 28,000 are more preferable.
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.

  When the resin composition for an adhesion auxiliary layer contains a polyamide resin, the content is a 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. 2 to 15 parts by weight, preferably 2 to 13 parts by weight, and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the solid content (including the inorganic filler (C)). When the content of the polyamide resin is 2 parts by mass or more, the adhesive strength with the conductor layer formed by the plating method tends to be excellent, and when it is 15 parts by mass or less, the interlayer insulating layer is roughened with an oxidizing agent. Furthermore, the surface roughness of the interlayer insulating layer tends to be suppressed, and the reflow heat resistance tends to be excellent.

<Method for Producing Multilayer Resin Film Having Resin Composition Layer for Interlayer Insulating Layer and Adhesion Auxiliary Layer>
As a method for producing a multilayer resin film having a resin composition layer for an interlayer insulating layer and an adhesion auxiliary layer, for example, a resin composition for an adhesion auxiliary layer in a varnish state is applied on a support and then dried. After forming the adhesion auxiliary layer on the support, the interlayer insulation layer resin composition in the state of varnish is coated on the adhesion auxiliary layer and then dried to obtain the resin composition for interlayer insulation layer The method of forming a physical layer is mentioned.
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 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.

  The method for applying the resin composition for the adhesion auxiliary layer and the resin composition for the interlayer insulating layer and the drying conditions are the same as the method and conditions that can be used for producing the resin composition film for the interlayer insulating layer of the present invention. is there.

[Multilayer printed wiring board]
The multilayer printed wiring board of the present invention is obtained using at least one selected from the group consisting of the resin film for interlayer insulation layers and the multilayer resin film of the present invention. That is, the resin film for interlayer insulation layers of the present invention is useful for multilayer printed wiring boards. Furthermore, the resin film for interlayer insulation layers of the present invention is useful for forming a buildup layer of a multilayer printed wiring board, particularly a buildup wiring board.
The multilayer printed wiring board of the present invention has, for example, 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).
Hereinafter, when simply referred to as “resin film”, both “interlayer insulating layer resin film” and “multilayer resin film” are used.

(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 resin film laminated in step (1) to form an insulating layer [hereinafter referred to as insulating layer forming step (2)].
(3) A step of drilling the circuit board on which the insulating layer has been formed in the step (2) [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 by a semi-additive method [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. Vacuum laminators include vacuum applicators manufactured by Nichigo-Morton Co., Ltd., vacuum press laminators manufactured by Meiki Seisakusho, roll-type dry coaters manufactured by Hitachi, Ltd., and vacuum laminators manufactured by Hitachi Chemical Electronics Co., Ltd. Can be mentioned.

When the protective film is provided on the resin film, the protective film is peeled off or removed, and then the resin film for an interlayer insulating layer of the present invention or the resin composition layer for the interlayer insulating layer of the multilayer resin film of the present invention is a circuit. The circuit board can be pressed and laminated while being pressed and heated so as to be in contact with the substrate. At this time, the support such as the organic resin film subjected to the release treatment may remain attached to the resin film of the present invention.
The laminate is prepared, for example, by preheating a resin film and a circuit board as necessary, and then a pressure bonding temperature of 60 to 140 ° C. and a pressure bonding pressure of 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”. When a multilayer resin film is used, the insulating layer formed here is a layer composed of a cured product of the resin composition layer for an interlayer insulating layer and a cured product of the adhesion auxiliary layer.
The heat curing may be performed in two stages. For example, the first stage is 100 to 200 ° C. for 5 to 30 minutes, and the second stage is 140 to 220 ° C. for 20 to 80 minutes. . When using a support such as an organic resin film that has been subjected to a mold release treatment, the support of an organic resin film that has been subjected to a mold release process is used from the viewpoint of preventing contamination of impurities such as dust. It is preferable to perform thermosetting with the body attached. When a support such as an organic resin film subjected to a release treatment is used, it is possible to prevent the rubber from being mixed in this way, but on the other hand, the release tends to increase due to the release treatment being performed. It is in. However, if the thermosetting resin composition (resin composition for an interlayer insulating layer), the resin film for an interlayer insulating layer, and the multilayer resin film of the present invention are used, this repellency can be effectively suppressed.
In addition, you may peel this support body after the said thermosetting.

  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.

In the roughening treatment step (4), the surface of the insulating layer is roughened with an oxidizing agent. At this time, so-called “smear” generated when via holes, through holes and the like are formed in the insulating layer and the circuit board may be removed by an oxidizing agent. That is, the roughening process 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 oxidizer widely used for roughening an insulating layer in the production of multilayer printed wiring boards by a 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. The metal for plating should be selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. Copper and nickel are preferable, and copper is more preferable.
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 120 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. Further, the interlayer insulating layer may be cured by this annealing treatment.
Here, before any of the steps (2) to (5), a support such as an organic resin film subjected to a release treatment may be peeled off, and any of the steps (3) to (5) may be performed. It is preferable to peel off and remove a support such as an organic resin film which has been subjected to a mold release treatment before that.
In the circuit forming step (6), a semi-additive process (SAP) is used as a method of patterning the conductor layer to form a circuit. After a plating resist pattern is formed on the conductor layer (seed layer) formed in the conductor layer forming step (5), the circuit is grown by performing plating such as electrolytic copper plating. Thereafter, the plating resist is removed, and then the seed layer between the circuits is etched to complete the wiring board.

  The surface of the conductor layer (circuit) thus produced may be roughened (blackened). 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 was patterned 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, etc. The thing in which the conductor layer (circuit) was formed is mentioned.
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 Pattern processing on one or both sides of a cured product that has a formed interlayer insulation layer and has a conductor layer (circuit) patterned on one or both sides thereof, and a cured product formed by laminating and curing the resin film of the present invention Those having a conductive layer (circuit) formed are also included in the circuit board of the present invention.
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 roughening treatment in advance by blackening treatment or the like as described above.

[A] 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.
After coating the resin composition varnish 1 for an adhesive film obtained above on PET (Teijin DuPont Films, trade name: G2, film thickness: 50 μm) as a support film, it was dried, A resin 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 4
In Example 1, adhesive films 2 to 6 and 8 to 12 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 on 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 A support film 2 having a thickness of 60 μm obtained by drying 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.
After coating the resin varnish A obtained above on PET (Teijin DuPont Films, trade name: G2, film thickness: 50 μm), which is a support film, It dried and obtained the support body film 2 whose film thickness is 60 micrometers.

Next, a resin composition varnish for an adhesive film to be coated 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 12 were evaluated by the following methods.

(Preparation and test method for adhesive film handling test)
The obtained adhesive films 1 to 12 were cut into a size of 500 mm × 500 mm to prepare Samples 1 to 12 for handling property test of the adhesive film.
Using the samples 1 to 12 for handling test of the produced adhesive film, the handling properties were 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 1-12 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 coated and dried resin that adhered to the protective film side or 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 cracked in the coated and dried resin was regarded 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 12 was cut into a size of 200 mm × 200 mm, the protective film was peeled off, and a batch-type vacuum and 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 the samples cut into a width of 3 mm and a length of 8 mm were designated as thermal expansion coefficient measurement samples 1 to 12.

The thermal expansion coefficient was measured by the following method using the produced samples 1 to 12 for measuring the thermal expansion coefficient.
Using the thermomechanical analyzer manufactured by Seiko Instruments Inc., the obtained samples 1 to 12 for measuring the thermal expansion coefficient were heated to 240 ° C. at a temperature rising 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 12 with the protective film peeled off so that the resin composition layer faces the circuit surface side of the circuit board, the 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 12 were obtained.

Using the fabricated embedding evaluation substrates 1 to 12, the embedding property was 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 evaluation substrates 1 to 12 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)
N-673-80M: Cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name, solvent; MEK, solid content concentration 80% 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, and an interlayer insulating layer having a low thermal expansion coefficient after curing can be provided.

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

The weight average molecular weight of the cyanate prepolymer, the weight average molecular weight and the 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.

Production Example 1
(Synthesis of cyanate prepolymer B)
In a 5 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, “Arocy (registered trademark) B-10”, a bisphenol A type bifunctional cyanate resin (manufactured by Huntsman, molecular weight 278) 35.8 g, 45.8 g of p- (α-cumyl) phenol (Mitsui Chemical Fine Co., Ltd., molecular weight 212) and 1,303 g of toluene were used as 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., 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 B (weight average molecular weight: about 3,200) dissolved in toluene was prepared by additionally blending toluene so that the solid content concentration of the reaction solution was 70% by mass.

[Preparation of support auxiliary layer with support]
Production Example 2
The composition is blended according to the blending composition shown in Table 2 (the numerical values in the table are parts by mass of the solid content, and in the case of a solution (excluding organic solvents) or a dispersion, it is the solid content conversion amount)). Was dissolved until dissolved, and dispersed by bead milling to obtain a varnish-like resin composition for an auxiliary adhesion layer (solid content concentration: 25% by mass).
The resin composition for an adhesion auxiliary layer obtained above was subjected to a release treatment on a PET film “Purex (registered trademark) NR-1” having a thickness of 38 μm (support, manufactured by Teijin DuPont Films Ltd.). The film was coated using a die coater so that the film thickness after drying was 3 μm, and an adhesion auxiliary layer with a support, in which the film thickness of the adhesion auxiliary layer was 3 μm, was obtained. The raw materials used are shown in Table 2.

The material used for the mixing | blending of the resin composition for adhesion auxiliary layers of Table 2 is shown below.
[(A) Epoxy resin]
NC-3000-H: biphenylaralkyl structure-containing novolak type epoxy resin (“NC-3000-H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 289 g / eq, solid content concentration: 100 mass%)
[(B) Curing agent]
Cyanate prepolymer B: Cyanate prepolymer B synthesized in Production Example 1
[(C) Inorganic filler]
Aerosil R972: fumed silica (“Aerosil (registered trademark) R972” manufactured by Nippon Aerosil Co., Ltd., specific surface area: 100 m ² / g, solid content concentration: 100 mass%)
[(D) Resin having a polysiloxane skeleton]
BYK-310: Polyester-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)

[(E) Phenoxy resin]
YX7200B35: phenoxy resin (“jER (registered trademark) YX7200B35” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 3,000 to 16,000 g / eq, solid content concentration 35 mass%, MEK cut)
[(F) Curing accelerator]
・ TPP: Triphenylphosphine (Tokyo Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
[Other resins; Polyamide resins]
BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (“BPAM-155” manufactured by Nippon Kayaku Co., Ltd., number average molecular weight: 26,000, weight average molecular weight: 110,000, solid content concentration: 100% by mass ) Previously dissolved in dimethylacetamide so that the solid content concentration is 10% by mass.

[Production of multilayer resin film]
(Reference) Examples 1-9, (Reference) Comparative Examples 1-4
The composition is blended according to the composition shown in Table 3 (the numerical values in the table are parts by mass of the solid content, and in the case of a solution (excluding an organic solvent) or a dispersion, it is the solid content equivalent amount)), and cyclohexanone ( Gordo Co., Ltd.) was added as an additional organic solvent and dispersed by bead mill treatment to obtain a varnish-like resin composition for an interlayer insulating layer (solid content concentration: about 70% by mass).
The resin composition for an interlayer insulating layer obtained above was applied on the adhesion auxiliary layer of the adhesion auxiliary layer with support obtained in Production Example 2 using a die coater and dried at 100 ° C. for 1.5 minutes. Thus, a resin composition layer for an interlayer insulating layer having a film thickness of 37 μm was formed, and a multilayer resin film (thickness 40 μm) having the resin composition layer for an interlayer insulating layer and an adhesion auxiliary layer was obtained.
Each evaluation was performed according to the following method using this multilayer resin film. The results are shown in Table 3.

[(1) Evaluation of presence or absence of repellent]
The application state (application state after drying) of the resin composition layer for an interlayer insulating layer formed on the surface of the adhesion auxiliary layer was visually evaluated. The resin composition layer for the interlayer insulating layer formed on the surface of the adhesion auxiliary layer was observed for the presence of an insufficient film thickness portion (so-called repellency). “A” was not observed, and “C” was observed. ".

[(2) Evaluation of surface roughness after desmear treatment]
In evaluating the surface roughness, a substrate for surface roughness evaluation was prepared by the following procedure. In addition, when repelling occurred in the evaluation of (1) above, a surface roughness evaluation substrate was produced using a region where repelling did not occur.
Both sides of “MCL-E-700G” (Type R, double-sided copper-clad laminate, thickness 0.8 mm, each copper foil thickness 18 μm, manufactured by Hitachi Chemical Co., Ltd.) are attached to “MEC etch bond CZ-8101” (MEC Co., Ltd.) The copper foil was roughened by etching 1 μm. Using the two multilayer resin films obtained in each example on both sides of the obtained laminate, one sheet is laminated on each side on the resin composition layer side for the interlayer insulating layer to provide a support. With the PET film still attached, heat curing was performed at 180 ° C. for 60 minutes. Thereafter, the PET film was peeled off.
The obtained sample was cut into a length of 60 mm (X direction) and a width of 120 mm (Y direction) as a test piece, and the test piece was used as a swelling liquid “Swelling Dip Securigant P” (manufactured by Atotech Japan Co., Ltd.). Immerse at 70 ° C. for 5 minutes, then immerse in the roughening solution “Consulate Rate Compact CP” (NaMnO ₄ -containing oxidizing agent, manufactured by Atotech Japan Co., Ltd.) for 20 minutes at 80 ° C., then neutralize the “reduction conditioner” The substrate was subjected to desmear treatment by immersing it in Securigant P500 (manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes to produce a substrate for surface roughness evaluation.
(2-1) About the obtained surface roughness evaluation substrate, a specific contact type surface roughness meter “WykoNT9100” (trade name, manufactured by Bruker AXS Co., Ltd.) was used, and the internal lens was 1 × and the external lens 50 was used. The surface roughness of the adhesion assisting layer was measured using a double to obtain the arithmetic average roughness (Ra). Arithmetic average roughness (Ra) is an average value obtained by measuring the average roughness at five locations for an arbitrary portion in the substrate for surface roughness measurement (however, a region where via holes are not formed by laser). . The arithmetic average roughness (Ra) is preferably as small as possible from the gist of the present invention.
(2-2) On the other hand, about the obtained surface roughness evaluation substrate, the surface of the adhesion auxiliary layer was observed with a scanning electron microscope (SEM) (magnification: 1,000 times), and an unroughened portion. When there was no “A”, it was evaluated as “A”, and when there was, it was evaluated as “C”.

[(3) Evaluation of reflow heat resistance]
In evaluating reflow heat resistance, a reflow heat resistance evaluation substrate was prepared according to the following procedure. When repelling occurred in the evaluation of (1) above, a reflow heat resistance evaluation substrate was produced using a region where repelling did not occur.
The surface roughness evaluation substrate prepared in (2) above was subjected to electroless plating to form a 0.8 μm thick plating, and further subjected to electrolytic plating to form a 20 μm plated. Next, the substrate was heat-treated at 190 ° C. for 120 minutes and cut into a size of 50 mm × 50 mm, thereby preparing 10 reflow heat resistance evaluation substrates.
For each of the 10 substrates for evaluation of reflow heat resistance, 30 air reflow furnaces “TAR30-366PN” (manufactured by Tamura Corporation, feed rate 0.61 m / min) set so that the maximum temperature is 260 ° C. The average number of passes until blistering occurred was used as an index of reflow heat resistance. It shows that it is excellent in reflow heat resistance, so that this average frequency | count is large, Preferably it is 10 times or more, More preferably, it is 15 times or more, More preferably, it is 20 times or more.

It shows below about the component as described in Table 3.
[(A) Epoxy resin]
N-673: Cresol novolak type epoxy resin (“EPICLON (registered trademark) N-673” manufactured by DIC Corporation, solid content concentration: 100 mass%, epoxy equivalent: 210 g / eq)
JER157S70: bisphenol A novolac type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 210 g / eq, solid content concentration: 100% by mass)

[(B) Curing agent]
-Cyanate prepolymer B: Cyanate prepolymer B synthesized in Production Example 1, component (b2)-BA3000S: Prepolymer of bisphenol A type cyanate resin ("Primaset BA3000S" manufactured by Lonza), (b2) component-HPC- 8000-65T: active ester resin (“EPICLON (registered trademark) HPC-8000-65T” manufactured by DIC Corporation, solid content concentration 65% by mass, toluene cut product), component (b1)

[(C) Inorganic filler]
SO-C2: spherical silica treated with aminosilane coupling agent (manufactured by Admatechs, volume average particle size 0.5 μm, solid content concentration 100% by mass)

[(D) Resin having a polysiloxane skeleton]
BYK-310: Polyester-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)
BYK-330: Polyether-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)
BYK-307: polyether-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)
・ Borchi Gol LA2: Polyether-modified polydimethylsiloxane (manufactured by Borchers)
・ Borchi Gol LA200: Polyether-modified polydimethylsiloxane (manufactured by Borchers)
Borchi Gol 1376: phenyl-modified polydimethylsiloxane (manufactured by Borchers)
(For comparison with component (d))
-LHP-90: Vinyl polymer (Enomoto Kasei Co., Ltd.), surface conditioner-LHP-95: Acrylic polymer (Enomoto Kasei Co., Ltd.), surface conditioner

[(E) Phenoxy resin]
YX7200B35: phenoxy resin (“jER (registered trademark) YX7200B35” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 3,000 to 16,000 g / eq, solid content concentration 35 mass%, MEK cut)

[(F) Curing accelerator]
Phosphorus curing accelerator: addition reaction product of tris (p-methylphenyl) phosphine and 1,4-benzoquinone synthesized with reference to JP 2011-179008 A (solid content concentration 100% by mass), the following (f -1).

・ Cobalt naphthenate: (Wako Pure Chemical Industries, Ltd., solid content concentration 6 mass%, mineral spirit solution), metal-based curing accelerator

From the results shown in Table 3, the resin composition for an interlayer insulating layer used in (Reference) Examples 1 to 9 has no repelling after coating, and (Reference) the multilayer resin film obtained in Examples 1 to 9 Then, the surface roughness of the adhesion assistance layer after desmear processing was small, and the unroughened site | part did not exist. Furthermore, (reference) The multilayer resin films obtained in Examples 1 to 9 were excellent in reflow heat resistance.
On the other hand, in the resin composition for interlayer insulation layers used in (Reference) Comparative Examples 1, 2, and 4, there are those having repelling after coating, and (Reference) In the multilayer resin film obtained in Comparative Example 2, The surface roughness of the adhesion auxiliary layer after the desmear treatment was large, and an unroughened portion was present. Furthermore, the (referential) multilayer resin film obtained in Comparative Example 2 was poor in reflow heat resistance.
Although the content of the resin having the (d) polysiloxane skeleton in the “adhesion auxiliary layer” is the same in (Reference) Comparative Example 2 and (Reference) Example 1, (Reference) in Comparative Example 2 As a result, an unroughened portion was present on the surface of the adhesion auxiliary layer. This must be considered that there was an influence of the resin composition for interlayer insulation layers.

[Preparation of support auxiliary layer with support]
Production Example 3
The composition is blended according to the blending composition shown in Table 4 (the numerical values in the table are parts by mass of the solid content, and in the case of a solution (excluding organic solvents) or a dispersion, it is a solid content conversion amount)). Was dissolved until dissolved, and dispersed by bead milling to obtain a varnish-like resin composition for an auxiliary adhesion layer (solid content concentration: 25% by mass).
The resin composition for an adhesion auxiliary layer obtained above was subjected to a release treatment on a PET film “Purex (registered trademark) NR-1” having a thickness of 38 μm (support, manufactured by Teijin DuPont Films Ltd.). The film was coated using a die coater so that the film thickness after drying was 3 μm, and an adhesion auxiliary layer with a support, in which the film thickness of the adhesion auxiliary layer was 3 μm, was obtained. Table 4 shows the raw materials used.

The material used for the mixing | blending of the resin composition for adhesion auxiliary layers of Table 4 is shown below.
[(A) Epoxy resin]
NC-3000-H: biphenylaralkyl structure-containing novolak type epoxy resin (“NC-3000-H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 289 g / eq, solid content concentration: 100 mass%)
[(B) Curing agent]
-HPC-8000-65T: Active ester resin (“EPICLON (registered trademark) HPC-8000-65T” manufactured by DIC Corporation, solid content concentration 65 mass%, toluene cut product)
PAPS-PN2: A phenol novolac-based curing agent containing a triazine ring (manufactured by Asahi Organic Materials Co., Ltd.)
[(C) Inorganic filler]
Aerosil R972: fumed silica (“Aerosil (registered trademark) R972” manufactured by Nippon Aerosil Co., Ltd., specific surface area: 100 m ² / g, solid content concentration: 100 mass%)
[(D) Resin having a polysiloxane skeleton]
BYK-310: Polyester-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)

[(E) Phenoxy resin]
YX7200B35: phenoxy resin (“jER (registered trademark) YX7200B35” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 3,000 to 16,000 g / eq, solid content concentration 35 mass%, MEK cut)
[(F) Curing accelerator]
-4-dimethylaminopyridine: Tokyo Chemical Industry Co., Ltd. make and dilute to 10% with methyl ethyl ketone.
[Other resins; Polyamide resins]
BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (“BPAM-155” manufactured by Nippon Kayaku Co., Ltd., number average molecular weight: 26,000, weight average molecular weight: 110,000, solid content concentration: 100% by mass ) Previously dissolved in dimethylacetamide so that the solid content concentration is 10% by mass.

[Production of multilayer resin film]
(Reference) Examples 10-12, (Reference) Comparative Examples 5-6
The composition is blended according to the composition shown in Table 4 (the numerical values in the table are parts by mass of the solid content, and in the case of a solution (excluding an organic solvent) or a dispersion, it is a solid content conversion amount)), and cyclohexanone ( Gordo Co., Ltd.) was added as an additional organic solvent, and then dispersed by bead mill treatment to obtain a varnish-like resin composition for an interlayer insulating layer (solid content concentration: about 66 to 69% by mass).
The resin composition for an interlayer insulating layer obtained above was applied on the adhesion auxiliary layer of the adhesion auxiliary layer with support obtained in Production Example 3 using a die coater and dried at 100 ° C. for 1.5 minutes. Thus, a resin composition layer for an interlayer insulating layer having a film thickness of 37 μm was formed, and a multilayer resin film (thickness 40 μm) having the resin composition layer for an interlayer insulating layer and an adhesion auxiliary layer was obtained.
Each evaluation was performed by the same method as in the (Reference) Example 1 using the multilayer resin film. The results are shown in Table 5.

The components described in Table 5 are shown below.
[(A) Epoxy resin]
NC-3000-H: Aralkyl novolac type epoxy resin having a biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., solid content concentration: 100% by mass, epoxy equivalent: 289 g / eq)
JER828: bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, solid content concentration 100% by mass, epoxy equivalent: 185 g / eq)

[(B) Curing agent]
-LA-7054: Triazine-containing phenol novolac resin (DIC Corporation "Phenolite (registered trademark) LA-7054"), component (b3)-HPC-8000-65T: Active ester resin (DIC Corporation "EPICLON ( (Registered trademark) HPC-8000-65T ", solid content concentration 65% by mass, toluene cut product), component (b1) PAPS-PN2: a phenol novolac-based curing agent containing a triazine ring (manufactured by Asahi Organic Materials Co., Ltd., Solid content concentration 100% by mass, Mw / Mn = 1.17), component (b3)

[(C) Inorganic filler]
SO-C2: spherical silica treated with aminosilane coupling agent (manufactured by Admatechs, volume average particle size 0.5 μm, solid content concentration 100% by mass)

[(D) Resin having a polysiloxane skeleton]
BYK-310: Polyester-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)
BYK-330: Polyether-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd.)

[(E) Phenoxy resin]
YX7200B35: phenoxy resin (“jER (registered trademark) YX7200B35” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 3,000 to 16,000 g / eq, solid content concentration 35 mass%, MEK cut)

[(F) Curing accelerator]
4-Dimethylaminopyridine: manufactured by Kanto Chemical Co., Inc., diluted to 10% with methyl ethyl ketone.

From the results of Table 5, the resin composition for an interlayer insulating layer used in (Reference) Examples 10 to 12 has no repellency after coating, and (Reference) the multilayer resin film obtained in Examples 10 to 12 Then, the surface roughness of the adhesion assistance layer after desmear processing was small, and the unroughened site | part did not exist. Furthermore, (reference) The multilayer resin films obtained in Examples 10 to 12 were excellent in reflow heat resistance.
On the other hand, the resin composition for an interlayer insulating layer used in (Reference) Comparative Example 5 has cissing after coating, and (Reference) the multilayer resin film obtained in Comparative Example 6 has a desmear treatment. The surface roughness of the adhesion auxiliary layer was large, and unroughened portions were present. In addition, the multilayer resin film obtained in (Reference) Comparative Example 6 was poor in reflow heat resistance. Although the content of the resin having the (d) polysiloxane skeleton in the “adhesion auxiliary layer” is the same in (Reference) Comparative Example 6 and (Reference) Example 10, (Reference) in Comparative Example 6 As a result, an unroughened portion was present on the surface of the adhesion auxiliary layer. This must be considered that there was an influence of the resin composition for interlayer insulation layers.

Claims (1)

(A) a novolak-type phenol resin having a dispersion ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) of 1.05 to 1.8;
(B) an epoxy resin represented by the following general formula (1);
(C) an inorganic filler;
A resin composition layer formed by layering a resin composition containing
The average particle diameter of the inorganic filler (C) in the resin composition layer is 0.1 μm or more,
(C) The adhesive film for multilayer printed wiring boards whose content of an inorganic filler is 20-95 mass% among resin solid content.

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