TW201809190A - Adhesive film to be used in multilayer printed circuit board - Google Patents

Abstract

Provided is an adhesive film to be used in a multilayer printed circuit board and exhibiting excellent uneven-surface embedding properties even when densely packing a silica filler. Specifically, this adhesive film has a resin composition layer obtained by forming a layer, on a support film, of a resin composition that contains: (A) a novolac phenolic resin in which the dispersity (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.05-1.8; (B) an epoxy resin represented by general formula (1); and (C) an inorganic filler material. Therein, the average particle diameter of the (C) inorganic filler material in the resin composition layer is 0.1[mu]m or higher, and the content of the inorganic filler material constitutes 20-95 mass% of the solid content of the resin.

Description

Adhesive film for multilayer printed wiring board

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

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

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

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

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

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

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

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

[Problems to be Solved by the Invention]

[a] If the silicon dioxide filler is highly filled in order to reduce the CTE of the build-up layer, the build-up material tends to be difficult to be buried in 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 with a build-up material so that the unevenness becomes smaller. If the silica filler is highly filled in order to reduce the CTE of a building material, it tends to be difficult to satisfy these requirements.

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

[b] In addition, in a conventional resin composition for an interlayer insulating layer for a multilayer printed wiring board, it is difficult to achieve a high heat resistance and insulation reliability and excellent handleability when formed into a film.

The second invention is made to solve the above-mentioned problems, and an object thereof is to provide a resin film for an interlayer insulating layer formed using a thermosetting resin composition having high heat resistance and insulation reliability, and excellent operability at the time of film formation, And a multilayer resin film having the resin film for an interlayer insulating layer and a support, a multilayer printed wiring board, and a method for manufacturing the same. [Means for solving problems]

[a] The present inventors made repeated efforts to solve the first problem, and as a result, found that by using a resin composition containing a specific novolac-type phenol resin, a specific epoxy resin, and a specific inorganic filler Object, the first problem can be solved, and the present invention has been completed. That is, the first invention provides the following adhesive film.

(1) An adhesive film for a multilayer printed wiring board, comprising a resin composition layer formed by forming a layer of the following resin composition on a support film, the resin composition comprising: (A) novolac-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); and (C) An inorganic filler; and the average particle diameter of the (C) inorganic filler in the resin composition layer is 0.1 μm or more, and the content of the (C) inorganic filler is 20% to 95% by mass of the resin solid content.

[Chemical 1]

(Where p is an integer from 1 to 5)

[b] The present inventors made repeated efforts in order to solve the second problem, and as a result, found that the thermosetting resin composition containing an epoxy resin, a hardener, an inorganic filler, and an antioxidant was combined by combining A specific hardener and a specific antioxidant can solve the second problem and complete the present invention. In addition, it has been found that in a thermosetting resin composition containing an epoxy resin, a hardener, an inorganic filler, and a specific compound, the second problem can also be solved by combining a specific hardener and a specific compound, so that The present invention has been completed. That is, the second invention provides the following [1] to [23].

[1] A resin film for an interlayer insulating layer, which is formed using a thermosetting resin composition containing (a) an epoxy resin, (b) a hardener, (c) an inorganic filler, and (d) an antioxidant, The (b) hardener includes a group selected from the group consisting of (b1) an active ester-based hardener, (b2) a cyanate-based hardener, and (b3) a triazine ring-containing phenol novolak-based hardener. At least one, and (d) the antioxidant is a hindered phenolic antioxidant. [2] The resin film for an interlayer insulating layer according to the above [1], wherein the hindered phenol-based antioxidant includes a compound selected from a compound having a group represented by the following general formula (dI) and the following general formula At least one of the group consisting of the compound represented by (dII). [Chemical 2] (In formula (dI), R ^d1 , R ^d2, and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. At least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms. Base) (In formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms. R ^d6 , R ^d7, and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. (At least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms) [3] The resin film for an interlayer insulating layer according to the above [2], which has the general formula (dI The compound of the group represented by) is a compound represented by any one of the following general formula (dI-1) to (dI-3). [Chemical 4] (In formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22, and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Among them , At least one of R ^d11 and R ^d12 and at least one of R ^d21 and R ^d22 represent an alkyl group having 1 to 8 carbon atoms. X ¹ and X ² each independently represent a monovalent to trivalent organic group. N ¹ and n ² are each independently an integer of 1 to 3) [Chem. 5] (In formula (dI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms. Y represents -COOCH _2- , -COOCH ₂ CH _2- ) [4] As described in [3] The resin film for an interlayer insulating layer according to the above, wherein the hindered phenol-based antioxidant is selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2) And at least one of the groups of which the molecular weight is 1,500 or less. [5] A resin film for an interlayer insulating layer, comprising (a) an epoxy resin, (b) a hardener, (c) an inorganic filler, and (d ′) selected from the group consisting of the following formula (dI) At least one of the group consisting of a compound of a group and a compound represented by the following general formula (dII), wherein the (b) hardener includes a compound selected from (b1) an active ester-based hardener and (b2) cyanic acid At least one of the group consisting of an ester-based hardener and (b3) a triazine ring-containing phenol novolak-based hardener. [Chemical 6] (In formula (dI), R ^d1 , R ^d2, and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. At least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms. Base) (In formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms. R ^d6 , R ^d7, and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. (At least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms) [6] The resin film for an interlayer insulating layer according to the above [5], which has the general formula (dI The compound of the group represented by) is a compound represented by any one of the following general formula (dI-1) to (dI-3). [Chemical 8] (In formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22, and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Among them , At least one of R ^d11 and R ^d12 and at least one of R ^d21 and R ^d22 represent an alkyl group having 1 to 8 carbon atoms. X ¹ and X ² each independently represent a monovalent to trivalent organic group. N ¹ and n ² are each independently an integer of 1 to 3) (In formula (dI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms. Y represents -COOCH _2- , -COOCH ₂ CH _2- ) [7] As described in [6] The resin film for an interlayer insulating layer described in the above, wherein the compound having a group represented by the general formula (dI) is selected from a compound represented by the general formula (dI-1) and the general formula (dI- 2) At least one of the group consisting of the compound represented by the compound and has a molecular weight of 1,500 or less. [8] The resin film for an interlayer insulating layer according to any one of [1] to [7], wherein the total number of functional groups of the (b) hardener is relative to (a) an epoxy resin. The ratio of the total number of epoxy groups [(b) the total number of functional groups of the hardener / (a) the total number of epoxy groups of the epoxy resin] is 0.2 to 2. [9] The resin film for an interlayer insulating layer according to any one of the above [1] to [8], wherein (a) the epoxy resin has a resin selected from a bisphenol A type epoxy resin and a naphthalene type epoxy resin; At least one of the group consisting of an aralkyl novolac epoxy resin and a cresol novolac epoxy resin having a biphenyl skeleton. [10] The resin film for an interlayer insulating layer according to any one of the above [1] to [9], wherein the (b) hardener includes (b2) a cyanate-based hardener. [11] The resin film for an interlayer insulating layer according to any one of the above [1] to [9], wherein the (b) hardener comprises a resin selected from (b1) an active ester hardener and (b3) At least one of the group consisting of a phenol novolac-based hardener containing a triazine ring. [12] The resin film for an interlayer insulating layer according to any one of the above [1] to [9] and [11], wherein the (b3) phenol novolak-based hardener containing a triazine ring has a triazine At least one of a cyclic phenol novolac resin and a triazine ring-containing cresol novolac resin. [13] The resin film for an interlayer insulating layer according to any one of the above [1] to [12], wherein the content of the inorganic filler is (c) 30 based on the solid content of the thermosetting resin composition. Mass% to 90% by mass. [14] The resin film for an interlayer insulating layer according to any one of the above [1] to [13], wherein (c) the inorganic filler contains a material selected from the group consisting of spherical silica and fused silica At least one of the groups, and the volume average particle diameter is 0.01 μm to 5 μm. [15] The resin film for an interlayer insulating layer according to any one of the above [1] to [14], wherein the thermosetting resin composition further contains (e) a phenoxy resin. [16] The resin film for an interlayer insulating layer according to the above [15], wherein the (e) phenoxy resin has an alicyclic structure. [17] The resin film for an interlayer insulating layer according to any one of the above [1] to [16], which is used for a multilayer printed wiring board. [18] The resin film for an interlayer insulating layer according to any one of the above [1] to [16], which is used for forming a build-up layer of a multilayer printed wiring board. [19] A multilayer resin film comprising the resin film for an interlayer insulating layer according to any one of [1] to [16], and a support. [20] The multilayer resin film according to [19], wherein the support is an organic resin film, the thickness of the organic resin film is 10 μm to 70 μm, and the thickness of the resin film for the interlayer insulating layer is It is 1 μm to 80 μm. [21] A multilayer printed wiring board using the resin film for an interlayer insulating layer as described in any one of [1] to [16], and as described in [19] or [20] It is obtained by at least one of the group consisting of the described multilayer resin film. [22] A semiconductor package obtained by mounting a semiconductor element on the multilayer printed wiring board according to [21]. [23] A method for manufacturing a multilayer printed wiring board using the resin film for an interlayer insulating layer according to any one of [1] to [16], and the method according to [19] or [20] The method for manufacturing a multilayer printed wiring board of the multilayer resin film described in the above includes the following steps: (1) Laminating the resin film for an interlayer insulating layer and the multilayer resin film on one or both sides of a circuit board Steps; (2) a step of thermally curing the laminated resin film in step (1) to form an insulating layer; (3) a step of making holes in the circuit substrate having the insulating layer formed in step (2); 4) a step of removing the dross; (5) a step of forming a conductor layer on the surface of the insulating layer obtained in step (4) by plating; and (6) a step of forming on the conductor layer by a semi-additive method Circuit steps. [Effect of the invention]

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

[b] According to the second invention, it is possible to provide a resin film for an interlayer insulating layer formed using a thermosetting resin composition having high heat resistance and insulation reliability and excellent operability when forming a film, and the interlayer insulation A multilayer resin film for a layer resin film and a support, a multilayer printed wiring board, and a method for manufacturing the same.

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

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

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

The (A) novolac-type phenol resin as described above can be produced by, for example, the production method described in Japanese Patent No. 4,283,793. That is, using a phenol compound and an aldehyde compound as raw materials, a phosphoric acid compound as an acid catalyst, and a non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent, the two-layer separation state formed by these is, for example, mechanically stirred, It is agitated and mixed by ultrasonic waves, and becomes a two-layer (organic phase and water phase) mixed turbid heterogeneous reaction system (phase separation reaction). The reaction of a phenol compound and an aldehyde compound proceeds to synthesize a condensate (resin). Next, for example, a water-insoluble organic solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, etc.) is added and mixed, the condensate is dissolved, the stirring is stopped, and the mixture is allowed to stand and separated into an organic phase ( An organic solvent phase) and an aqueous phase (aqueous phosphoric acid solution phase) can be recovered by removing the aqueous phase. On the other hand, after washing and / or neutralizing the organic phase with hot water, the organic solvent can be recovered by distillation. ) Novolac phenol resin. Since the method for producing a novolac phenol resin uses a phase separation reaction, the stirring efficiency is extremely important. From the aspect of reaction efficiency, it is desirable to miniaturize the two phases in the reaction system so as to increase the surface area of the interface as much as possible. This promotes the conversion of phenolic compounds to resins.

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

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

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

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

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

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

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

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

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

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

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

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

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

<(B) Epoxy resin> (B) The epoxy resin is an epoxy resin represented by the following general formula (1).

[Chemical 10]

(Where p is an integer from 1 to 5)

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

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

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

(C) The average particle diameter of the inorganic filler is 0.1 μm or more, and from the viewpoint of obtaining excellent embedding properties, it is preferably 0.2 μm or more, and more preferably 0.3 μm or more. From the viewpoint of embedding property, the content of the inorganic filler having an average particle diameter of less than 0.1 μm is preferably 3 vol% or less, more preferably 1 vol% or less, and more preferably no average particle diameter, based on the solid content. Inorganic filler less than 0.1 μm. In addition, the (C) inorganic filler may be used singly or in combination of two or more kinds, and those having different average particle diameters may be mixed and used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[b] Second invention Next, a resin film for an interlayer insulating layer, a multilayer resin film, a multilayer printed wiring board and a method for manufacturing the same according to the second invention will be described. [Resin Film for Interlayer Insulation Layer] The thermosetting resin composition [hereinafter referred to as a resin composition for an interlayer insulation layer] used in the formation of the resin film for an interlayer insulation layer of the present invention contains (a) a ring as described above. Oxygen resin (hereinafter, also referred to as "(a) component"), (b) the specific hardener described below (hereinafter, also referred to as "(b) component"), (c) inorganic filler (hereinafter, also referred to as "(C) component"), and (d) the following specific antioxidant (hereinafter, also referred to as "(d) component") or (d ') the following specific compound (hereinafter, also referred to as "( d ') ingredients "). The resin film for an interlayer insulating layer is also commonly referred to as an interlayer insulating film.

<Resin composition for interlayer insulation layer> [(a) Epoxy resin] (a) The epoxy resin is not particularly limited, and for example, an epoxy resin having two or more epoxy groups in one molecule can be preferably cited. Examples of such (a) epoxy resin include a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, and a glycidyl ester type epoxy resin. Among these epoxy resins, a glycidyl ether type epoxy resin is preferable.

(A) Epoxy resins are also classified according to the main skeleton. Among the various types of epoxy resins, they are further classified as bisphenol A epoxy resins (preferably bisphenol A liquid epoxy resins). , Bisphenol F epoxy resin, bisphenol S epoxy resin and other bisphenol epoxy resins; phenol novolac epoxy resin, alkylphenol novolac epoxy resin, cresol novolac epoxy resin Novolac epoxy resins such as naphthol alkylphenol copolymerized novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, aralkyl novolac epoxy resin, etc. Stilbene epoxy resin; triazine skeleton epoxy resin; fluorene skeleton epoxy resin; naphthalene epoxy resin; triphenylmethane epoxy resin; biphenyl epoxy resin; xylene Epoxy resins; alicyclic epoxy resins such as dicyclopentadiene epoxy resins. (A) The epoxy resin may be used alone or in combination of two or more. Examples of the aralkyl novolac epoxy resin include an aralkyl cresol copolymerized novolac epoxy resin having a naphthol skeleton, and an aralkyl novolac epoxy resin having a biphenyl skeleton. It is an aralkyl novolak epoxy resin having a biphenyl skeleton.

Among these, from the viewpoint of heat resistance, insulation reliability, and operability at the time of film formation, it is preferably selected from the group consisting of a bisphenol-type epoxy resin and a novolac-type epoxy resin. At least one, more preferably selected from the group consisting of bisphenol A epoxy resin, cresol novolac epoxy resin, aralkyl novolac epoxy resin, and bisphenol A novolac epoxy resin At least one. Furthermore, the aralkyl novolak-type epoxy resin is more preferably an aralkyl novolak-type epoxy resin having a biphenyl skeleton.

When two or more (a) epoxy resins are used in combination, a bisphenol A type epoxy resin and an aralkyl novolak type epoxy resin (particularly an aralkyl novolak type having a biphenyl skeleton) are preferred. Epoxy resin), or a combination of a cresol novolac epoxy resin and a bisphenol A novolac epoxy resin. When combined with a bisphenol A-type epoxy resin and an aralkyl novolak-type epoxy resin (especially an aralkyl novolak-type epoxy resin having a biphenyl skeleton), the heat resistance and insulation are reliable. From the viewpoints of properties and operability at the time of film formation, the content ratio (bisphenol A-type epoxy resin / aralkyl novolac-type epoxy resin) is preferably 15/85 to 50/50, and more preferably It is 15/85 to 45/55, and particularly preferably 20/80 to 40/60. When used in combination with a cresol novolac epoxy resin and a bisphenol A novolac epoxy resin, from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, Its content ratio (cresol novolac epoxy resin / bisphenol A novolac epoxy resin) is preferably 50/50 to 85/15, more preferably 45/55 to 85/15, and even more preferably 55 / 45 ～ 75/25.

Here, the aralkyl novolak-type epoxy resin having a biphenyl skeleton refers to an aralkyl novolak-type epoxy resin containing an aromatic ring of a biphenyl derivative in a molecule, and examples thereof include the following: An epoxy resin or the like of the structural unit represented by the formula (a1).

[Chemical 11] In the general formula (a1), R ^a1 represents a hydrogen atom or a methyl group.

Content of the structural unit represented by General formula (a1) in the epoxy resin containing the structural unit represented by General formula (a1) from a viewpoint of heat resistance, insulation reliability, and handleability at the time of film formation. It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass. Examples of the epoxy resin containing a structural unit represented by the general formula (a1) include epoxy resins represented by the following general formula (a1-1).

[Chemical 12] In the general formula (a1-1), R ^a1 is the same as described above, and m ¹ represents an integer of 1 to 20. A plurality of R ^a1 may be the same as or different from each other, and are preferably the same.

The bisphenol A novolac epoxy resin can be represented by the following general formula (a2). [Chemical 13] In the general formula (a2), m ² represents an integer of 1 to 10.

In addition, from the viewpoint of improving the operability of the resin film for an interlayer insulating layer, (a) the epoxy resin may contain a liquid epoxy resin (hereinafter, simply referred to as a liquid epoxy resin in some cases) at room temperature. ). The liquid epoxy resin is not particularly limited, and examples thereof include bifunctional liquid epoxy resins such as a bisphenol A type liquid epoxy resin. In the case where (a) the epoxy resin contains a liquid epoxy resin, the content of the liquid epoxy resin is smaller than (a) the epoxy resin in terms of improving the operability of the resin film for an interlayer insulating layer. It is preferably 10% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 10% by mass to 40% by mass.

(A) A commercially available epoxy resin can also be used. Commercially available (a) epoxy resins can be listed as "NC-3000-H", "NC-3000-L", "NC-3100", "NC-3000" (the above are manufactured by Nippon Kayaku Co., Ltd.) , Trade name, aralkyl novolac epoxy resin with biphenyl skeleton), "NC-7000-L" (manufactured by Nippon Kayaku Co., Ltd., trade name, naphthol novolac epoxy resin), " jER828 "(Mitsubishi Chemical Co., Ltd., trade name, bisphenol A type epoxy resin)," jER157S70 "(Mitsubishi Chemical Co., Ltd., trade name, bisphenol A novolac type Epoxy) etc.

From the viewpoints of heat resistance, insulation reliability, and workability when forming a film, (a) the epoxy equivalent of the epoxy resin is preferably 150 g / eq to 500 g / eq, and more preferably 150 g / eq. eq ～ 400 g / eq, particularly preferably 170 g / eq ～ 350 g / eq, particularly preferably 200 g / eq ～ 320 g / eq, and may be 170 g / eq ～ 230 g / eq, or 250 g / eq to 320 g / eq. Here, the epoxy equivalent is the resin mass (g / eq) of each epoxy group, and it can be measured according to the method prescribed in Japanese Industrial Standards (JIS) K 7236 (2001). Specifically, by using an automatic titration device "GT-200" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 2 g of epoxy resin was weighed in a 200 ml beaker, and 90 ml of formazan was added dropwise. After dissolving the ethyl ethyl ketone in the ultrasonic scrubber, 10 ml of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide were added, and the solution was determined by titration with a 0.1 mol / L perchloric acid / acetic acid solution. Out.

From the viewpoints of heat resistance, insulation reliability, and workability when forming a film, with respect to 100 parts by mass of the solid content of the resin composition for an interlayer insulating layer (here, except for (c) an inorganic filler), The content of the (a) epoxy resin in the resin composition for an interlayer insulating layer is preferably 20 parts by mass to 80 parts by mass, more preferably 30 parts by mass to 70 parts by mass, and even more preferably 35 parts by mass to 60 parts by mass. Here, the "solid content" in the present invention is a non-volatile component other than a volatile component such as an organic solvent, unless otherwise specified, and indicates a component that does not volatilize and remains when the thermosetting resin composition is dried. It also includes liquid, sugar-thin and waxy ones at room temperature. Here, in this specification, the room temperature means 25 ° C.

[(B) Hardener] In the present invention, (b) the hardener is selected from (b1) an active ester-based hardener, (b2) a cyanate-based hardener, and (b3) a triazine ring-containing phenol novolak. At least one of the group consisting of a hardener. When two or more of the above (b1) to (b3) are used, there is no particular limitation, and from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, it is preferably ( b1) a combination of an active ester-based hardener and (b2) a cyanate-based hardener, (b1) a combination of an active ester-based hardener and (b3) a phenol novolak-based hardener containing a triazine ring. In addition, two or more kinds of (b1) may be used in combination, two or more kinds of (b2) may be used in combination, or two or more kinds of (b3) may be used in combination.

((B1) Active ester hardener) (b1) The active ester hardener is not particularly limited as long as it functions as a hardener for (a) an epoxy resin and has an active ester. When (b1) an active ester-based hardener is contained, the dielectric loss tangent tends to be reduced. (B1) Active ester hardeners can be used: phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxyl ester compounds, etc., which have highly reactive ester groups and have the hardening effect of epoxy resins. Compounds.

(B1) The active ester hardener is preferably a compound having two or more active ester groups in one molecule, more preferably one compound obtained from a compound having a polycarboxylic acid and an aromatic compound having a phenolic hydroxyl group. Aromatic compounds having two or more active ester groups, particularly preferred are aromatic compounds having more than two ester groups in the molecule of the aromatic compound, and the aromatic compound has at least two in one molecule. A compound of the above carboxylic acid and an aromatic compound having a phenolic hydroxyl group. In addition, the (b1) active ester-based hardener may include a linear or multi-branched polymer. If the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with (a) epoxy resin and (b2) cyanate resin can be improved. An aromatic ring compound can improve heat resistance. Particularly from the viewpoint of heat resistance and the like, the (b1) active ester-based hardener 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, pyromellitic acid, and the like. Among these compounds, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and m-benzene is more preferred. Dicarboxylic acid, terephthalic acid. Examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalin, methylated bisphenol A, and methylated bisphenol F. , Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl Diphenol, phenol novolac, etc. Among these compounds, from the viewpoints of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol are preferred. S, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Ketones, resorcinols, trimerols, dicyclopentadienyl diphenols, phenol novolacs, more preferably catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, pyroglycerol, dicyclopentadienyl diphenol, phenol novolac, especially Preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentane Dienyl diphenol, phenol novolac, particularly preferred are dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac. Dicyclopentadienyl diphenol, phenol novolac, best Dicyclopentadiene diphenol. Examples of the thiol compound include benzenedithiol and triazinedithiol.

(B1) As the active ester-based hardener, the active ester-based hardener disclosed in Japanese Patent Laid-Open No. 2004-277460 can be used, and a commercially available product can also be used. Commercially available (b1) active ester-based hardeners include compounds containing a dicyclopentadienyl diphenol structure, an acetic acid compound of a phenol novolac, a benzamidine compound of a phenol novolac, and the like. A compound containing a dicyclopentadienyl diphenol structure is preferred. Specifically, compounds containing a dicyclopentadienyl diphenol structure include: "EXB9451" (active ester group equivalent: about 220 g / eq), "EXB9460", "EXB9460S-65T", "HPC-8000- "65T" (equivalent ester group equivalent: about 223 g / eq) (the above is manufactured by DIC Corporation, trade name), and the acetic acid compound of phenol novolac can be listed as "DC808" (Mitsubishi Chemical) Co., Ltd., active ester group equivalent: about 149 g / eq). Examples of benzamidine compounds of phenol novolak include "YLH1026" (Mitsubishi Chemical Co., Ltd., active ester group equivalent: about 200). g / eq) and so on.

(B1) The manufacturing method of an active ester hardening | curing agent is not specifically limited, It can manufacture by a well-known method. Specifically, it can be obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.

((B2) Cyanate-based hardener) (b2) A cyanate-based hardener may be a known cyanate resin. For example, the cyanate resin may include two or more cyanic acid in one molecule. Based cyanate resin. (B2) The cyanate-based hardener specifically includes 2,2-bis (4-cyanophenyl) propane [bisphenol A-type cyanate resin], and bis (4-cyanophenyl) ) Ethane [bisphenol E-type cyanate resin], bis (3,5-dimethyl-4-cyanophenyl) methane [tetramethylbisphenol F-type cyanate resin], 2, 2 -Bis (4-cyanophenyl) -1,1,1,3,3,3-hexafluoropropane [hexafluorobisphenol A-type cyanate resin] and other bisphenol-type cyanate resins; phenol addition Dicyclopentadiene-based cyanate resins such as cyanate ester compounds that form dicyclopentadiene polymers; novolak-based phenolic novolac-based cyanate ester compounds, cresol novolac-based cyanate ester compounds Cyanate resins; α, α'-bis (4-cyanophenyl) -m-isopropylbenzene; prepolymers of these cyanate resins (hereinafter, also referred to as "cyanate prepolymers"物 ") and so on. These may be used alone or in combination of two or more. Among these, from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, a cyanate resin represented by the following general formula (b2-I) and the following general formula ( The cyanate resin represented by b2-IV) and these prepolymers are more preferably a cyanate resin represented by the following general formula (b2-I) and these prepolymers.

[Chemical 14]

In the general formula (b2-I), R ^b1 represents an alkylene group having 1 to 3 carbon atoms which can be substituted with a halogen atom, a sulfur atom, the following general formula (b2-II) or the following general formula (b2-III ). R ^b2 and R ^b3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The two R ^b2 or two R ^b3 may be the same as or different from each other, and are preferably the same.

[Chemical 15]

In the general formula (b2-II), R ^{b 4} represents an alkylene group having 1 to 3 carbon atoms. The two R ^b4s may be the same as or different from each other, and are preferably the same.

[Chemical 16]

[Chemical 17]

In the general formula (b2-IV), R ^b5 represents a hydrogen atom or a C 1-3 alkyl group which may be substituted with a halogen atom. n represents an integer of 1 or more. The plurality of R ^b5 may be the same as or different from each other, and are preferably the same.

Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^b1 in the general formula (b2-I) include methylene, ethylidene, 1,2-propylidene, and 1,3-propylidene. And 2,2-propylidene (-C (CH ₃ ) _2- ). Among these, from the viewpoints of heat resistance, insulation reliability, and handleability at the time of film formation, methylene or 2,2-propylidene (-C (CH ₃ ) _2- ) is preferred, More preferred is 2,2-propylidene (-C (CH ₃ ) _2- ). Examples of the halogen atom that replaces the alkylene group having 1 to 3 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^b4 in the general formula (b2-II) include methylene, ethylidene, 1,2-propylidene, and 1,3-propylidene. And 2,2-propylidene (-C (CH ₃ ) _2- ). Among these groups represented by R ^b1 , from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, methylene or 2,2-propenyl (-C ( CH ₃ ) _2- ), more preferably 2,2-propenyl (-C (CH ₃ ) _2- ). 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 methyl, ethyl, propyl, and butyl.

Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^{b 5} in the general formula (b2-IV) include a methyl group, an ethyl group, and a propyl group. Examples of the halogen atom that replaces the alkyl 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-IV), n represents an integer of 1 or more, and from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, it is preferably 1 to 7, and more preferably 1 to 4. .

The so-called cyanate prepolymer refers to a polymer in which cyanate resins form a triazine ring through cyclization reaction, and mainly includes a trimer, a pentamer, and a heptamer of a cyanate ester compound. , Nine polymer, eleven polymer, etc. In this cyanate ester prepolymer, the conversion rate of the cyanate group is not particularly limited, and from the viewpoint of obtaining good solubility in organic solvents, it is preferably 20% by mass to 70% by mass, and more preferably 30% by mass. % To 65% by mass. 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, a prepolymer of a dicyanate compound having two cyano groups in one molecule is more preferable from the viewpoints of heat resistance, insulation reliability, and operability at the time of film formation, and it is more preferable. It is a prepolymer of a cyanate resin represented by the general formula (b2-I), and it is particularly preferred that at least a part of 2,2-bis (4-cyanophenyl) propane is triazinated to become three Polymer prepolymer (see formula (b2-V) below).

[Chemical 18]

The weight average molecular weight (Mw) of the cyanate ester prepolymer is not particularly limited. From the viewpoint of solubility and workability of the organic solvent, it is preferably 500 to 4,500, more preferably 600 to 4,000, and particularly preferably 1,000 to 4,000, particularly preferably 1,500 to 4,000. When the weight-average molecular weight (Mw) of the cyanate prepolymer is 500 or more, crystallization of the cyanate prepolymer is suppressed, and the solubility in organic solvents tends to be good. 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) and using a standard polystyrene calibration curve. Specifically, The measurement was performed according to the method described in the examples.

The cyanate ester prepolymer may be obtained by prepolymerizing the cyanate resin in the presence of a monofunctional phenol compound. When manufacturing a cyanate ester prepolymer, by blending a monofunctional phenol compound, unreacted cyanate groups in the obtained hardened product can be reduced, and therefore, there is a tendency that the moisture resistance and electrical characteristics are excellent. Examples of the monofunctional phenol compound include alkyl-substituted phenol compounds such as p-nonylphenol, p-third butylphenol, p-third pentylphenol, and p-third octylphenol; p- (α -Cumyl) phenol, mono-, di-, or tri- (α-methylbenzyl) phenol and other phenol-based compounds represented by the following general formula (b2-VI). These may be used alone or in combination of two or more.

[Chemical 19]

In the general formula (b2-VI), R ^b6 and R ^{b 7} 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 as or different from each other, and are preferably the same.

As for the usage amount of the monofunctional phenol compound, it is preferred that the equivalent ratio (hydroxyl / cyano group) of the phenolic hydroxyl group of the monofunctional phenol compound to the cyanate group of the cyanate resin is 0.01 to 0.30 The amount is more preferably 0.01 to 0.20, and even more preferably 0.01 to 0.15. When the use amount of the monofunctional phenol compound is within the above range, in addition to a tendency to obtain a sufficiently low dielectric loss tangent, particularly in a high frequency band, there is also a tendency to obtain good moisture resistance.

The manufacturing method of a cyanate ester prepolymer is not specifically limited, A well-known manufacturing method can be applied. The cyanate ester prepolymer can be preferably produced by, for example, reacting the dicyanate compound with the monofunctional phenol compound. A compound having a group represented by -OC (= NH) -O- is formed by a reaction of a dicyanate compound and a monofunctional phenol compound (that is, an imino carbonate), and then the imino group is formed. When the carbonates are reacted with each other or the imide carbonate and the dicyanate compound are reacted, the monofunctional phenol compound is removed, and on the other hand, a cyanate ester prepolymer having a triazine ring is obtained. In the reaction, for example, the dicyanate compound and the monofunctional phenol compound may be mixed and dissolved in the presence of a solvent such as toluene. While maintaining the temperature at 80 ° C to 120 ° C, zinc naphthenate may be added as necessary. And other reaction promoters.

Commercially available cyanate ester resins can also be used. 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 triazinated to form trimers. . Commercial products of bisphenol A-type (2,2-bis (4-hydroxyphenyl) propane-type) cyanate resins can also use "Primaset BADCy" (manufactured by Lonza) , Trade name), "Arocy B-10" (manufactured by Huntsman, trade name), etc. In addition, a commercially available product of a bisphenol E-type (1,1-bis (4-hydroxyphenyl) ethane-type) cyanate resin may be "Arocy L10" (Huntsman ) Made by the company, trade name), "Primaset LECy" (made by Lonza, trade name), etc., 2,2'-bis (4-cyanate-3,5-form As a commercially available product of a phenylphenyl) ethane-based cyanate resin, "Primaset METHYLCy" (manufactured by Lonza) can be used. As a commercially available product of the novolac-type cyanate resin, "Primaset PT30" (a product of Lonza, trade name), etc., which is a phenol-novolac-type cyanate resin, can also be used. A commercially available prepolymer of a cyanate resin may be a "Primaset BA200" (Lonza) manufactured by prepolymerizing a bisphenol A type cyanate resin. (Brand name), "Primaset BA230S" (manufactured by Lonza, trade name), etc., "Primaset BA3000", etc. can also be used. In addition, "Arocy XU-371" (manufactured by Huntsman, trade name), and "Arocy" which is a cyanate resin containing a dicyclopentadiene structure can also be used. (Arocy) XP71787.02L "(manufactured by Huntsman, trade name)," Primaset DT-4000 "(manufactured by Lonza, trade name)," Prima (Primaset DT-7000 "(manufactured by Lonza, trade name), etc.

((B3) A phenol novolak-based hardener containing a triazine ring) (b3) A phenol novolak-based hardener containing a triazine ring The novolak-type phenol resin used as a hardener for an epoxy resin can contain three Those who have a hydrazine ring. The novolak phenol resin containing a triazine ring is a product in which an aminotriazine ring structure and a phenol structure are randomly bonded through a methylene group. The triazine ring-containing phenol novolak-based hardener is preferably at least one of a triazine ring-containing phenol novolak resin and a triazine ring-containing cresol novolak resin. A triazine ring-containing novolac-type phenol resin can be produced, for example, by using the production method described in Japanese Patent Laid-Open No. 2002-226556. That is, it can be produced by subjecting a phenol compound, an aminotriazine compound, and an aldehyde compound to a co-condensation reaction to a substantially neutral degree in the presence or absence of a weakly basic catalyst such as an alkylamine.

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

Examples of the 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, p-formaldehyde, trioxane, acetaldehyde, paraldehyde, and propionaldehyde. Among these compounds, paraformaldehyde is preferred from the viewpoint of the reaction rate. These compounds may be used alone or in combination of two or more.

The blending molar ratio (F / P) of the aldehyde compound (F) and the phenol compound (P) is preferably 0.33 or more, more preferably 0.40 to 1.0, and even more preferably 0.50 to 0.90. By setting the blending molar ratio (F / P) within the range, excellent yield can be obtained. The nitrogen atom content in the (b3) triazine ring-containing phenol novolac-based hardener is preferably 8% to 30%, and more preferably 8% to 20%.

(B3) A commercially available phenol novolac-based hardener containing a triazine ring can be used. Examples include "PAPS-PN2" (made by Asahi Organic Materials Industry Co., Ltd., trade name), and "PAPS-PN3" (Asahi You Made by Machinery Industry Co., Ltd., trade name), "Phenolite LA-1356" (manufactured by DIC Corporation, trade name), "Phenolite LA-7054" (including Triazine's phenol novolac resin, manufactured by DIC Corporation, trade name), "Phenolite LA-3018" (triazine-containing cresol novolac resin, DIC) Co., Ltd., trade name).

The (b) curing agent of the resin composition for an interlayer insulating layer used in the present invention may be cured with an epoxy resin other than the curing agent (b1) to (b3) as long as the effect of the present invention is not inhibited. Agent (hereinafter also referred to as "epoxy resin hardener"). Examples of the epoxy resin hardener include phenol resins that do not contain a triazine ring, phosphorus-containing phenol compounds, acid anhydride compounds, amine compounds, and hydrazine compounds. Examples of the phenol resin that does not contain a triazine ring include a novolac-type phenol resin, a resol-type phenol resin, and the like. The phosphorus-containing phenol compound is a compound having two or more phenolic hydroxyl groups and containing a phosphorus atom, and examples thereof include 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphorus Heterophenanthrene-10-oxide [HCA-HQ or HCA-HQ-HS (manufactured by Sanguang Co., Ltd., trade name)] and the like. Examples of the acid anhydride compound include phthalic anhydride, benzophenone tetracarboxylic dianhydride, and methylnadic acid. Examples of the amine compound include dicyandiamine, diaminodiphenylmethane, and guanyl urea. Among these epoxy resin hardeners, a phenol resin and a phosphorus-containing phenol compound not containing a triazine ring are preferred from the viewpoint of improving reliability, and a phosphorus-containing phenol is more preferred from the viewpoint of flame retardancy. Compound. In addition, in the present invention, those having a function as a hardener and also having other functions are preferentially classified as having a function as a hardener and classified as "hardener". For example, the phosphorus-containing phenol compound has a function as a hardener and a function as a flame retardant, and is classified as a hardener.

(B) The hardener may be composed of (b2) a cyanate-based hardener, or may be selected from the group consisting of (b1) an active ester-based hardener and (b3) a triazine ring-containing phenol novolak-based hardener. At least one of the group. In particular, if it contains at least one selected from the group consisting of (b1) an active ester-based hardener and (b3) a triazine ring-containing phenol novolak-based hardener, a phosphorus-containing phenol compound mentioned later The effect of suppressing the ease of gelation is large, so it is preferable. That is, when it is desired to use a phosphorus-containing phenol compound having an effect as a hardener and also a flame retardant effect, a combination of (b1) an active ester-based hardener and (b3) a triazine ring-containing phenol novolac is used in combination. At least one of the group consisting of a varnish-based hardener suppresses gelation and maintains the operability at the time of film formation. From the same viewpoint, the (b) hardener is preferably one containing (b3) a phenol novolak-based hardener containing a triazine ring.

The content of (b1) the active ester-based hardener, (b2) the cyanate-based hardener, and (b3) the triazine ring-containing phenol novolac-based hardener in the (b) hardener is not particularly limited. When the (b1) component is used in combination with the (b2) component or the (b3) component, from the viewpoint of dielectric characteristics, the total amount of the (b1) component to (b3) component used is (b1) The component is preferably 40% by mass to 70% by mass, and more preferably 50% by mass to 65% by mass. From the viewpoints of heat resistance, insulation reliability, and handleability at the time of film formation, the mass of the total amount of the (b1) component to (b3) component in the (b) curing agent is preferably 20% by mass. Above, more preferably 40% by mass or more, particularly preferably 50% by mass or more. The upper limit value is not particularly limited, and may be 100% by mass, 90% by mass, or 80% by mass.

From the viewpoints of heat resistance, insulation reliability, and handleability when forming a film, the content ratio of the (a) epoxy resin and (b) hardener in the resin composition for an interlayer insulating layer is preferably adjusted to : The ratio of the total number of functional groups of the (b) hardener to the total number of epoxy groups of the (a) epoxy resin [(b) total number of functional groups of the hardener / (a) epoxy resin The total number of epoxy groups] is 0.2 to 2. If the ratio is 0.2 or more, there is a tendency that the amount of unreacted epoxy groups in the obtained interlayer insulating layer can be reduced, and if it is 2 or less, the amount of (b) the curing agent does not become excessive. , Can suppress the tendency of the rise in curing temperature. From the same viewpoint, the ratio is more preferably 0.4 to 1.5.

[(C) Inorganic Filler] The resin composition for an interlayer insulating layer used in the present invention further contains (c) an inorganic filler. From the viewpoint of preventing the scattering of the resin and making the shape of the laser processing uniform when the laser processing is performed on the interlayer insulating layer formed by thermally curing the resin composition for the interlayer insulating layer, (c) the inorganic filler is very important. In addition, when the surface of the interlayer insulating layer is roughened with an oxidizing agent, it is important from the viewpoint that a moderately roughened surface can be formed and a conductive layer having excellent adhesion strength can be formed by plating. Select from the viewpoints.

(C) Examples of inorganic fillers include silicon dioxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Barium titanate, strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these compounds, from the viewpoints of thermal expansion coefficient, operability of varnish, and insulation reliability, silicon dioxide is preferred, and spherical silica and fused silica are particularly preferred. The inorganic fillers may be used singly or in combination of two or more kinds.

From the viewpoint of forming fine wiring, (c) the inorganic filler is preferably one having a small particle diameter. From the same viewpoint, (c) the inorganic filler is preferably one having a specific surface area of 3 m ² / g or more, and may be 3 m ² / g to 200 m ² / g, or 3 m ² / g to 130 m ² / g, or 3 m ² / g to 50 m ² / g, or 3 m ² / g to 20 m ² / g. The specific surface area can be determined by the Brunauer-Emmett-Teller (BET) method using physical adsorption at low temperature and low humidity of an inert gas. Specifically, a molecule having a known adsorption area such as nitrogen can be adsorbed on the surface of the powder particle at the temperature of liquid nitrogen, and the specific surface area of the powder particle can be obtained based on the amount of adsorption. In addition, from the viewpoint of obtaining a good embedding property of the circuit board and the viewpoint of insulation reliability, (c) the volume average particle diameter of the inorganic filler is preferably 0.01 μm to 5 μm, and more preferably 0.1 μm to 2 μm, particularly preferably 0.2 μm to 1 μm. When the volume average particle diameter is 100% of the total volume of the particles and the cumulative degree distribution curve of the particle diameter is obtained, the particle diameter of the point corresponding to 50% of the volume can be obtained by using the laser diffraction scattering method. It is measured by a distribution measuring device or the like. (C) Commercially available inorganic fillers can also be used. Examples include: "AEROSIL (registered trademark) R972" (made by Japan Aerosil Co., Ltd., a trade name for fumed silica). , Specific surface area is 110 ± 20 m ² / g) and “AEROSIL (registered trademark) R202” (manufactured by Japan Aerosil Co., Ltd., trade name, specific surface area is 100 ± 20 m ² / g), "PL-1" (made by Fuso Chemical Industry Co., Ltd., trade name, specific surface area is 181 m ² / g) as colloidal silicon dioxide, and "PL-7" (Fuso Chemical Industry Co., Ltd. Manufactured by the company, trade name, specific surface area is 36 m ² / g) and so on.

From the viewpoint of improving the moisture resistance of the obtained interlayer insulating layer, (c) the inorganic filler may be an inorganic filler that has been surface-treated with a surface-treating agent such as a silane coupling agent. Commercially available inorganic fillers that have been surface-treated with a surface-treating agent can also be used. Examples include the silica filler "SO-C2" treated with an amine-based silane coupling agent (Admatechs Co., Ltd.) (Product name, trade name), Silica dioxide filler "YC100C" (trade name, manufactured by Admatechs Co., Ltd.) treated with phenylsilane coupling agent, Silicon oxide filler "Sciqas series" (manufactured by Sakai Chemical Industry Co., Ltd., trade name, 0.1 μm grade), etc.

From the viewpoint of the laser processability of the obtained interlayer insulating layer and the bonding strength with the conductor layer, the interlayer insulation is relative to the solid content of the resin composition for the interlayer insulating layer (including (c) the inorganic filler itself). The content of the (c) inorganic filler in the layer resin composition is preferably 30% to 90% by mass, more preferably 30% to 70% by mass, and even more preferably 40% to 60% by mass. (C) When the content of the inorganic filler is 30% by mass or more with respect to the solid content of the resin composition for an interlayer insulating layer, a good laser processability tends to be obtained, and if it is 90% by mass or less, it is present and used. The conductive layer formed by the plating method tends to have excellent bonding strength.

[(D) Antioxidant] The (d) antioxidant contained in the resin composition for an interlayer insulating layer is a hindered phenol-based antioxidant. The hindered phenol antioxidant is a compound having a substituent in the ortho position of the phenolic hydroxyl group, and particularly a compound having a substituent having a large steric hindrance such as a third butyl group and a trimethylsilyl group. The resin composition for an interlayer insulation layer needs to contain an unhindered phenol-based antioxidant. When the unhindered phenol-based antioxidant is contained, the content of the unhindered phenol-based antioxidant is preferably 30% by mass of the content of the hindered phenol-based antioxidant Hereinafter, it is more preferably 15% by mass or less, particularly preferably 5% by mass or less, and also 0% by mass. (D) The antioxidant is a hindered phenol-based antioxidant, which can improve the workability when forming a film.

Examples of hindered phenolic antioxidants include 2,6-di-third-butyl-p-cresol (trade name: Yoshinox BHT), 4,4'-butylene bis- (6-third Butyl-3-methylphenol) (trade name: Yoshinox BB), 2,2'-methylenebis- (4-methyl-6-tert-butylphenol) (trade name : Yoshinox 2246G), 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol) (Trade name: Yoshinox 425), 2 1,6-Di-Third-butyl-4-ethylphenol (Trade name: Yoshinox 250), 1,1,3-tris (2-methyl-4-hydroxy-5-third Butylphenyl) butane (trade name: Yoshinox 930), n-octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate (Trade name: Tominox SS, IRGANOX 1076, IRGANOX 1076FD), pentaerythritol tetrakis [3- (3,5-di-third-butyl- 4-hydroxyphenyl) propionate] (Trade name: Tominox TT; IRGANOX 1010, IRGANOX 1010FF), triethylene glycol bis [3- (3-Third-butyl-4- Hydroxy-5-methylphenyl) propionate] (Trade name: Tominox 917; IRGANOX 245, IRGANOX 245FF), three (3,5 -Di-tertiary butyl-4-hydroxybenzyl) isocyanurate (trade name: Yoshinox 314; IRGANOX 3114), 1,6-hexanediol- Bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259), 2,4-bis- (n-octylsulfan Group) -6- (4-hydroxy-3,5-di-third-butylaniline) -1,3,5-triazine (Trade name: IRGANOX 565, Yi Lunuosi ( IRGANOX) 565DD), 2,2-thio-diethylidene bis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate] (Trade name: Elunox (IRGANOX) 1035FF), N, N'-hexamethylenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) ammonium propionate] (trade name: Elunox (IRGANOX) 1098), 1,3,5-trimethyl-2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene (brand name: Elunox (IRGANOX) 1330), bis (3,5-di-third-butyl-4-hydroxybenzylphosphonic acid ethyl ester) calcium (trade name: Yilu IRGANOX 1425WL), 2,4-bis [(octylthio) methyl] -o-cresol (trade name: IRGANOX 1520L), isooctyl-3- (3,5 -Di-third-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1135) and the like.

The hindered phenol-based antioxidant preferably contains at least one selected from the group consisting of a compound having a group represented by the following general formula (dI) and a compound represented by the following general formula (dII). The compound having a group represented by the following general formula (dI) may include a compound represented by the following general formula (dII). [Chemical 20] (In formula (dI), R ^d1 , R ^d2, and R ^d3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. At least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms. Base) (In formula (dII), R ^d4 and R ^d5 each independently represent an alkyl group having 1 to 8 carbon atoms. R ^d6 , R ^d7, and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. , At least one of R ^d6 , R ^d7 and R ^d8 represents an alkyl group having 1 to 8 carbon atoms)

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^d1 , R ^d2 and R ^d3 in formula (dI) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Third butyl, n-hexyl, n-octyl and the like. Among these, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, methyl, ethyl, n-propyl, and third butyl are particularly preferred, and methyl is particularly preferred. Group, ethyl, third butyl. At least one of R ^d1 and R ^d2 represents an alkyl group having 1 to 8 carbon atoms. It may be a combination of R ^d1 being an alkyl group having 1 to 8 carbon atoms, and R ^d2 being a hydrogen atom. It may also be a combination of R ^d1 being a hydrogen atom and R ^d2 being an alkyl group having 1 to 8 carbon atoms, or it may be R ^d1 And R ^d2 are both an alkyl group having 1 to 8 carbon atoms.

In formula (dII), the alkyl groups having 1 to 8 carbon atoms represented by R ^d4 , R ^d5 , R ^d6 , R ^d7, and R ^d8 are described in the same manner as in the case of the aforementioned R ^d1 , R ^d2, and R ^d3 . The same goes for the best. At least one of R ^d6 , R ^d7, and R ^d8 represents an alkyl group having 1 to 8 carbon atoms, and preferably two of them represent an alkyl group having 1 to 8 carbon atoms. The combination of R ^d6 is a hydrogen atom, R ^d7 is a hydrogen atom, and R ^d8 is an alkyl group having 1 to 8 carbon atoms, or R ^d6 is a hydrogen atom, R ^d7 is an alkyl group having 1 to 8 carbon atoms, and R ^d8 is a combination of hydrogen atoms, or R ^d6 may be an alkyl group having 1 to 8 carbon atoms, R ^d7 is a hydrogen atom and R ^d8 is a combination of hydrogen atoms, or R ^d6 may be an alkyl group having 1 to 8 carbon atoms A combination of R ^d7 being a hydrogen atom and R ^d8 being a hydrogen atom, a combination of R ^d6 being an alkyl group having 1 to 8 carbon atoms, R ^d7 being an alkyl group having 1 to 8 carbon atoms, and R ^d8 being a combination of hydrogen atom, A combination of R ^d6 is an alkyl group having 1 to 8 carbon atoms, R ^d7 is a hydrogen atom, and R ^d8 is an alkyl group having 1 to 8 carbon atoms, or R ^d6 is a hydrogen atom and R ^d7 is a carbon number 1 A combination of an alkyl group of 8 to 8 and R ^d8 is an alkyl group of 1 to 8 carbons. R ^d6 , R ^d7, and R ^d8 may be alkyl groups having 1 to 8 carbon atoms.

The compound having a group represented by the general formula (dI) is preferably a compound represented by any one of the following general formulas (dI-1) to (dI-3). [Chemical 22]

(In formulas (dI-1) and (dI-2), R ^d11 , R ^d12 , R ^d13 , R ^d21 , R ^d22, and R ^d23 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Among them , At least one of R ^d11 and R ^d12 and at least one of R ^d21 and R ^d22 represent an alkyl group having 1 to 8 carbon atoms. X ¹ and X ² each independently represent a monovalent to trivalent organic group. N ¹ and n ² are each independently an integer of 1 to 3) The alkyl group having 1 to 8 carbon atoms will be described in the same manner as in the case of the above-mentioned R ^d1 , R ^d2, and R ^d3 , and the preferred ones are also the same. At least one of R ^d11 and R ^d12 represents an alkyl group having 1 to 8 carbon atoms. It can be a combination of R ^d11 being an alkyl group having 1 to 8 carbon atoms, and R ^d12 being a hydrogen atom, or a combination of R ^d11 being a hydrogen atom and R ^d12 being an alkyl group having 1 to 8 carbon atoms, or it can be R ^d11 And R ^d12 are both an alkyl group having 1 to 8 carbon atoms. It is preferable that R ^d11 and R ^d12 are both a combination of a third butyl group and R ^d13 is a hydrogen atom. Further, also preferred is a hydrogen atom as R ^d11, R ^d12 is alkyl having 1 to 8, R ^d13 is a combination of an alkyl group having 1 to 8 carbon atoms, also more preferably R ^d11 represents a hydrogen atom, R ^d12 It is a combination of a third butyl group and R ^d13 is a methyl group. At least one of R ^d21 and R ^d22 represents an alkyl group having 1 to 8 carbon atoms. A combination of R ^d21 being an alkyl group having 1 to 8 carbon atoms, and R ^d22 being a hydrogen atom, or a combination of R ^d21 being a hydrogen atom and R ^d22 being an alkyl group having 1 to 8 carbon atoms, or R ^d21 And R ^d22 are both an alkyl group having 1 to 8 carbon atoms. It is preferable that R ^d21 is a third butyl group, R ^d22 is an ethyl group, and R ^d23 is a hydrogen atom. In addition, R ^d13 is a hydrogen atom and has the same meaning as that without the substituent R ^d13 . In addition, R ^d23 is a hydrogen atom, and the meaning is the same as that without the substituent R ^d23 .

The monovalent to trivalent organic groups represented by X ¹ and X ² are not particularly limited, and examples thereof include an aliphatic hydrocarbon group, a amine bond-containing group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, and combinations thereof. Group. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Examples of the amine bond-containing group include-(CH ₂ ) ₂ -C (= O) -NH- (CH ₂ ) ₆ -NH-C (= O)-(CH ₂ ) ₂ -and the like. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of the heteroaromatic hydrocarbon group include an isocyanurate skeleton-containing group and the like. Specific examples of the group containing these combinations include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. n ¹ and n ² are each independently an integer of 1 to 3, or both of 1 and 2 are 3 and 3 are both.

[Chemical 23]

(In formula (dI-3), R ^d31 and R ^d32 each independently represent an alkyl group having 1 to 8 carbon atoms. Y represents -COOCH _2- , -COOCH ₂ CH _2- ) carbons represented by R ^d31 and R ^d32 The alkyl group having 1 to 8 will be described in the same manner as in the case of the above-mentioned R ^d1 , R ^d2, and R ^d3 , and the preferred ones are also the same. Among them, particularly preferred is tert-butyl.

The compound having a group represented by the general formula (dI) is preferably selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2) At least one of the groups has a molecular weight of 1,500 or less. More preferably, the molecular weight is at least one selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2), and the molecular weight is 1,000 or less, particularly preferably The molecular weight is 500 or less, and particularly preferably 400 or less.

[(D ') The following specific compound] The resin composition for an interlayer insulating layer may contain a (d') component instead of the (d) component. The component (d ') is at least one selected from the group consisting of a compound having a group represented by the general formula (dI) and a compound represented by the general formula (dII). Each of the groups in the general formula (dI) and the general formula (dII) has the same meaning as described above, and the same is also preferred. In particular, the compound having a group represented by the general formula (dI) is preferably a compound represented by any one of the general formula (dI-1) to (dI-3). The compound having a group represented by the general formula (dI) is preferably selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2). At least one of the groups has a molecular weight of 1,500 or less. More preferably, the molecular weight is at least one selected from the group consisting of a compound represented by the general formula (dI-1) and a compound represented by the general formula (dI-2), and the molecular weight is 1,000 or less, particularly preferably The molecular weight is 500 or less, and particularly preferably 400 or less.

From the viewpoints of heat resistance, insulation reliability, and handleability when forming a film, the component (d) or (d) in the resin composition for an interlayer insulating layer is compared to the solid content of the resin composition for an interlayer insulating layer. ') The content of the component is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, particularly preferably 0.05% by mass to 2% by mass, and particularly preferably 0.05% by mass to 1% by mass.

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

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

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

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

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

When the resin composition for an interlayer insulating layer contains (e) a phenoxy resin, the resin composition for the interlayer insulating layer contains 100 parts by mass of a solid content (here, except for (c) an inorganic filler) of the resin composition for the interlayer insulating layer. The content is preferably 0.2 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 3 to 20 parts by mass. When the content of the (e) phenoxy resin is 0.2 parts by mass or more, there is a tendency that the flexibility and handleability are excellent and the peel strength of the conductor layer is excellent. When the content of the phenoxy resin is 20 parts by mass or less, storage stability and fluidity are present. It is excellent and tends to obtain appropriate roughness.

[(F) Hardening Accelerator] The resin composition for an interlayer insulating layer may contain (f) a hardening accelerator from the viewpoint that hardening can be performed at a low temperature for a short time. (F) Examples of the hardening accelerator include metal-based hardening accelerators and organic hardening accelerators.

(Metal-based hardening accelerator) As the metal-based hardening accelerator, for example, an organometallic hardening accelerator can be used. The organometallic-based hardening accelerator has (b2) the promotion effect of the self-polymerization reaction of the cyanate-based curing agent and (a) the reaction action of the epoxy resin and (b) the curing agent. Examples of the organometallic hardening accelerator include transition metals, organometallic salts of Group 12 metals, and organometallic complexes. Examples of the metal include copper, cobalt, manganese, iron, nickel, zinc, and tin. Examples of the organometallic salt include carboxylates, and specific examples thereof include naphthenates such as cobalt naphthenate and zinc naphthenate; 2-ethyl cobalt such as cobalt 2-ethylhexanoate and zinc 2-ethylhexanoate Caproate; zinc octoate, tin octoate; tin stearate, zinc stearate, etc. Examples of the organometallic complex include chelate complexes such as acetoacetone complex, and specific examples thereof include organocobalt complexes such as cobalt (II) acetoacetate and cobalt (III) acetoacetate ; Organic copper complexes such as copper (II) acetamate; organic zinc complexes such as zinc (II) acetamate; organic iron complexes such as iron (III) acetamate; acetamidine pyruvate Organonickel complexes such as nickel (II); organomanganese complexes such as manganese (II) acetamidine. Among these complexes, from the viewpoints of hardenability and solubility, cobalt (II) acetamidine pyruvate, cobalt (III) acetamidine pyruvate, zinc (II) acetamidine pyruvate, and acetamidine are preferred. Iron (III) pyruvate, zinc naphthenate and cobalt naphthenate, more preferably zinc naphthenate. These may be used alone or in combination of two or more.

When the resin composition for an interlayer insulating layer contains a metal-based hardening accelerator, the content of the metal-based hardening accelerator is higher than that of the (b2) cyanate-based hardener in terms of reactivity and storage stability. It is preferably 1 mass ppm to 500 mass ppm, more preferably 10 mass ppm to 500 mass ppm, particularly preferably 50 mass ppm to 400 mass ppm, and particularly preferably 150 mass ppm to 300 mass ppm. The metal-based hardening accelerator can be prepared once or in a plurality of times.

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

Examples of the organic phosphorus compound include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and tricyclohexyl Phosphine, triphenylphosphine / triphenylborane complex, tetraphenylphosphonium tetraphenylborate, and the like. Among these, triphenylphosphine is preferable. Examples of the imidazole compound include 2-phenyl-4-methylimidazole and trimellitic acid 1-cyanoethyl-2-phenylimidazolium.

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

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

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

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

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

The resin composition for an interlayer insulating layer can be manufactured by mixing (a) component-(d) component, and mixing (e) component, (f) component, and other components as needed. As the mixing method, a known method can be applied, and for example, a bead mill or the like may be used for mixing.

<Thickness of Resin Film for Interlayer Insulation Layer> The thickness of the resin film for interlayer insulation layer can be determined by, for example, the thickness of a conductor layer formed on a printed wiring board. The thickness of the conductive layer is usually 5 μm to 70 μm. Therefore, the thickness of the resin film for the interlayer insulating layer is preferably 1 μm to 100 μm. From the viewpoint of reducing the thickness of the multilayer printed wiring board, the thickness is preferably 1 μm. ~ 80 μm, more preferably 1 μm to 70 μm, more preferably 15 μm to 70 μm, and most preferably 20 μm to 50 μm.

<Support> The resin film for an interlayer insulating layer of the present invention may be one formed on a support. Examples of the support include organic resin films, metal foils, and release paper. There is no particular limitation, and the support is preferably an organic resin film. Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate; polycarbonates Ester, polyimide, etc. Among these, PET is preferable from a viewpoint of price and operability. Examples of the metal foil include copper foil and aluminum foil. When using copper foil for a support body, a copper foil may be used as a conductor layer directly, and a circuit may be formed. In this case, rolled copper, electrolytic copper foil, or the like can be used for the copper foil. The thickness of the copper foil can be, for example, 2 μm to 36 μm. When a thin copper foil is used, a copper foil with a carrier may be used from the viewpoint of improving workability. One aspect of the present invention includes a multilayer resin film including the resin film for an interlayer insulating layer and the support. The multilayer resin film is preferably a multilayer resin film in which the support is an organic resin film, the thickness of the organic resin film is 10 μm to 70 μm, and the thickness of the resin film for the interlayer insulating layer is 1 μm to 80 μm. . This multilayer resin film may have a layer (resin composition layer for an interlayer insulating layer) including a resin film for an interlayer insulating layer, and an adhesive auxiliary layer.

Surface treatments such as a mold release treatment, a plasma treatment, and a corona treatment may be performed on these supports and a protective film described later. Examples of the release treatment include a release treatment using a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent. From the viewpoint of operability and economy, the thickness of the support is preferably 10 μm to 120 μm, more preferably 10 μm to 70 μm, more preferably 15 μm to 70 μm, and even more preferably 25 μm to 60 μm. . When manufacturing a multilayer printed wiring board, a support body is usually finally peeled or removed.

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

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

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

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

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

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

(1) A step of laminating the resin film of the present invention on one or both sides of a circuit board [hereinafter, referred to as a laminating step (1)]. (2) A step of forming an insulating layer by thermally curing the laminated resin film in step (1) [hereinafter, referred to as an insulating layer forming step (2)]. (3) A step of making a hole in the circuit board on which the insulating layer is formed in step (2) [hereinafter referred to as a hole-opening step (3)]. (4) A step of removing the dregs [hereinafter, referred to as a step of removing dregs (4)]. (5) After the slag removal step (4), a step of forming a conductor layer on the surface of the insulating layer by plating [hereinafter, referred to as a conductor layer forming step (5)]. (6) A step of forming a circuit on a 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 a circuit board using a vacuum laminator. Examples of the vacuum laminator include: a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., and a roller dry type manufactured by Hitachi Seisakusho Co., Ltd. Coating machine, vacuum laminator manufactured by Hitachi Chemical Co., Ltd., etc.

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

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

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

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

In the conductive layer forming step (5), the conductive layer is formed by plating on the surface of the insulating layer of the fixture having unevenness formed by the roughening treatment performed at the same time as the slag removing step (4). Examples of the plating method include an electroless plating method and an electrolytic plating method. The metal used for plating is not particularly limited as long as it can be used in plating. The metal used for the plating may be selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements, and copper is preferred. , Nickel, more preferably copper. Alternatively, a method may be adopted in which a plating resist having a pattern opposite to that of the conductor layer (wiring pattern) is formed in advance, and then the conductor layer (wiring pattern) is formed only by electroless plating. After the conductor layer is formed, an annealing treatment may be performed at 150 ° C to 200 ° C for 20 minutes to 120 minutes. By performing the annealing treatment, there is a tendency that the bonding strength between the interlayer insulating layer and the conductor layer is further improved and stabilized. In addition, the annealing treatment can also promote the hardening of the interlayer insulating layer. In the circuit forming step (6), a method of forming a circuit by patterning the conductor layer uses a semi-additive process (SAP). After forming a pattern of a plating resist on the conductive layer (seed layer) formed in the conductive layer forming step (5), plating such as electrolytic copper plating is performed to grow the circuit. Then, 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) produced as described above may be roughened (blackened). By roughening the surface of the conductor layer, there is a tendency that the adhesiveness with the resin contacting the conductor layer is improved. For roughening the conductor layer, "CZ-8100", "CZ-8101", and "CZ-5480" (all products manufactured by Mike (MEC) Co., Ltd.) are used as organic acid-based microetchants. Wait.

Examples of the circuit board used in the multilayer printed wiring board of the present invention include glass epoxy, metal substrate, polyester substrate, polyimide substrate, and bismaleimide triazine (BT) resin. On one or both sides of a substrate such as a substrate or a thermosetting polyphenylene ether substrate, a patterned conductor layer (circuit) is formed. In addition, the circuit board in the present invention also includes a multilayer printed wiring board having a conductor layer and an insulating layer alternately formed on one or both sides with a patterned conductor layer (circuit) on one side, and one side of the circuit board. Or an interlayer insulating layer formed of the resin film of the present invention on both sides, and a patterned conductor layer (circuit) on one or both sides thereof, a hardening formed by bonding and curing the resin film of the present invention Those who have patterned conductor layers (circuits) on one or both sides of the object. From the viewpoint of the adhesion of the interlayer insulating layer to the circuit substrate, as described above, the surface of the conductor layer of the circuit substrate may be roughened in advance by a blackening treatment or the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

[Table 1]

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

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

[b] Next, the second invention will be further described in detail, but the second invention is not limited in any way by these examples.

[Production of Resin Film for Interlayer Insulation Layer] Examples 1 to 9 and Comparative Examples 1 to 4 were prepared according to the blending compositions shown in Tables 2 to 4. [The values in the table are parts by mass of the solid content in the solution. (Except for organic solvents) or in the case of a dispersion liquid, the amount is equivalent to the solid content] The components are mixed and stirred. Then, it disperse | distributed by a bead mill process, and obtained the varnish-like resin composition for interlayer insulation layers. Using a die coater, the obtained resin composition for an interlayer insulating layer was coated on a PET film having a thickness of 38 μm as a support, and dried at 100 ° C. for 1.5 minutes, thereby obtaining a film thickness of 40 μm. Each evaluation of the multilayer resin film which has the resin film for interlayer insulation layers was performed according to the following method. The results are shown in Tables 2 to 4.

[(1) Evaluation of insulation reliability] The insulation reliability was evaluated by a high temperature and high humidity bias test. Using a laminator, at 110 ° C, the multilayer resin film having a thickness of 40 μm obtained in each example was attached to the comb-type copper electrode toward the interlayer insulating layer, and the test element group was attached to the test element group. , TEG) (commercial name: WALTS-KIT EM0101JY, manufactured by Walters, L / S = 10 μm / 10 μm) on a comb-shaped copper electrode. Then, the PET film as a support was peeled, and it heated in the oven at 190 degreeC for 2 hours, and cooled to room temperature, and obtained the sample for a measurement. A lead was attached to the electrode portion of the TEG of the obtained measurement sample by soldering, and a high temperature and high humidity bias test was performed [voltage: 5V (DC), test time: 200 hours, 130 ° C, 85% RH (using high temperature and high Wet machine (manufactured by ESPEC))]. At 200 hours of test time, if the resistance value remains above 1.0´10 ⁷ Ω, it can be said that the insulation reliability is excellent.

[(2) Evaluation of operability] After the multilayer resin film obtained in each example was left at room temperature (25 ° C) for 5 days, a resin film for an interlayer insulating layer was attached to a support, and in this state, The resin film side for the interlayer insulating layer was set to the outside (the PET film side was to the inside) and bent at 180 °, and the presence or absence of cracking was visually confirmed. Similarly, 20 pieces of the multilayer resin film were confirmed, and it was shown as "the number of multilayer resin films which cracked / 20".

[(3) Measurement of Glass Transition Temperature (Tg) (Evaluation of Heat Resistance)] As for the glass transition temperature (Tg), the support was peeled off from the multilayer resin film obtained in each example, and the resin film was used only as an interlayer insulating layer resin film. Five resin films were laminated, and the obtained laminate was thermally cured at 190 ° C for 120 minutes to obtain a cured product. The cured substrate was cut into a length of 40 mm (X direction), a width of 4 mm (Y direction), and a thickness of 200 μm (Z direction). As an evaluation substrate, a thermomechanical analysis device (TA instrument) was used for the evaluation substrate. (Manufactured by TA Instruments), Q400), and the thermomechanical analysis was performed by the compression method. Specifically, after the evaluation substrate was mounted on the device in the stretching direction (xy direction), the measurement was performed twice under the measurement conditions of a load of 5 mg and a temperature increase rate of 10 ° C / min, and the second measurement was determined. The Tg shown in the intersections of different wires in the thermal expansion curve is used as an index of heat resistance.

[Table 2] * 1 is the total number of functional groups of (b) hardener relative to the total number of functional groups of (a) epoxy resin. * 2 refers to the content of a hindered phenolic compound or an unhindered phenolic compound.

[table 3] * 1 is the total number of functional groups of (b) hardener relative to the total number of functional groups of (a) epoxy resin.

[Table 4] * 1 is the total number of functional groups of (b) hardener relative to the total number of functional groups of (a) epoxy resin.

Each component described in Tables 2 to 4 is shown below. [(A) Epoxy resin]-N-673: Cresol novolac type epoxy resin ("EPICLON (registered trademark) N-673" manufactured by DIC Corporation, solid content Concentration is 100% by mass, epoxy equivalent: 210 g / eq) • jER157S70: Bisphenol A novolac epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 210 g / eq, solid content Concentration is 100% by mass) ・ NC-3000-H: Aralkyl novolac epoxy resin with biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., solid content concentration is 100% by mass, epoxy equivalent: 289 g / eq) • jER828: bisphenol A type liquid epoxy resin (Mitsubishi Chemical Co., Ltd., solid content concentration of 100% by mass, epoxy equivalent: 185 g / eq)

[(B) Hardener] • BA230S: Prepolymer of bisphenol A type cyanate resin ("Primaset BA230S" manufactured by Lonza), (b2) ingredients, HPC- 8000-65T: Active ester resin ("EPICLON (registered trademark) HPC-8000-65T" manufactured by DIC), solid content concentration of 65% by mass, toluene cut product), ( b1) Ingredients LA-7054: Triazine-containing phenol novolac resin ("Phenolite (registered trademark) LA-7054" manufactured by DIC Corporation), (b3) ingredients, PAPS -PN2: Triazine-containing phenol novolac resin (manufactured by Asahi Organic Materials Industry Co., Ltd., solid content concentration is 100% by mass, Mw / Mn = 1.17), (b3) component, LA3018-50P: triazine-containing formazan Phenolic novolac resin ("Phenolite (registered trademark) LA3018-50P" manufactured by DIC Corporation), (b3) component (other hardener) ・ HCA-HQ-HS: Phosphorous Phenol compound (manufactured by Sanguang Co., Ltd.), 10- (2,5- Hydroxyphenyl) -9,10-dihydro-9-oxa-10-phospha phenanthrene-10-oxide

[(C) Inorganic Filler]-SO-C2: Spherical silica treated with amine silane coupling agent (manufactured by Admatechs Co., Ltd., volume average particle diameter is 0.5 μm, solid content Concentration is 100% by mass)

[(D) (d ') Hindered phenolic compound] ・ Yoshinox BB: 4,4'-butylene bis- (6-third butyl-3-methylphenol) (Mitsubishi Chemical ( (Mitsubishi Chemical) Co., Ltd.) ・ BHT: 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) ・ Yoshinox 425: 2,2'-Asia Methylbis- (4-ethyl-6-tert-butylphenol) (Mitsubishi Chemical Co., Ltd.) (Unhindered phenolic compound) ・ Bisphenol A: manufactured by Tokyo Chemical Industry Co., Ltd.

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

[(F) Hardening accelerator] • TPP: triphenylphosphine (manufactured by Kanto Chemical Co., Ltd.), organic hardening accelerator • zinc naphthenate: (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration is 8 % By mass, mineral spirits solution), metal hardening accelerator 2PZ-CNS-PW: trimellitic acid 1-cyanoethyl-2-phenylimidazolium (manufactured by Shikoku Chemical Industry Co., Ltd.)

[Additional organic solvent] ・ Cyclohexanone: Made by GODO Co., Ltd.

As can be seen from Tables 2 to 4, the resin films for interlayer insulating layers of Examples 1 to 9 have high heat resistance and insulation reliability, and are also excellent in operability. On the other hand, in the resin film for an interlayer insulating layer obtained in Comparative Examples 1 to 4, the insulation reliability and the operability were both inferior and could not be taken into consideration.

no

no

no

Claims (1)

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