KR20240017101A - Adhesive film for multilayer printed wiring boards - Google Patents

Abstract

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

Description

Adhesive film for multilayer printed wiring boards {ADHESIVE FILM FOR MULTILAYER PRINTED WIRING BOARDS}

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

In recent years, the demand for multilayer printed wiring boards used in electronic devices, communication devices, etc., not only for miniaturization, weight reduction, and high wiring density, but also for increased computational processing speed, has become stronger. In line with this, as a manufacturing method for multilayer printed wiring boards, a build-up manufacturing technology in which interlayer insulating layers are alternately stacked on the wiring layers of a circuit board is attracting attention.

In the build-up manufacturing technology, a method of manufacturing the interlayer insulating layer and the wiring layer involves mixing a resin for forming the interlayer insulating layer (hereinafter also referred to as “organic insulating resin”) and copper foil for forming the wiring layer using a press device. The organic insulating resin is heat-cured by pressing at a high temperature for a long period of time to obtain an interlayer insulating layer with copper foil, and then, if necessary, a via hole for interlayer connection is formed using a drill method, a laser method, etc., and then , the method of forming wiring using the so-called “subtractive method”, in which the copper foil is removed by etching while leaving the necessary portion, has been conventionally common.

However, in response to the above-mentioned demands for miniaturization, weight reduction, and higher wiring density of multilayer printed wiring boards, organic insulating resin and copper foil are pressed at high temperature for a short time using a vacuum laminator, and then organically dried at high temperature using a dryer, etc. The so-called “additive method”, which involves thermosetting an insulating resin, forming via holes for interlayer connections using drilling or laser methods as needed, and forming wiring layers in necessary areas by plating, has come to attract attention.

The organic insulating resin used in the build-up method is mainly a combination of an aromatic epoxy resin and a curing agent that has active hydrogen for the epoxy resin (e.g., phenol-based curing agent, amine-based curing agent, carboxylic acid-based curing agent, etc.). It has been used. The cured product obtained by curing using these curing agents has an excellent balance of physical properties, but the reaction between epoxy groups and active hydrogen generates highly polar hydroxy groups, resulting in increased water absorption, relative dielectric constant, and dielectric loss tangent. There was a problem that it caused a decline in . Additionally, when these curing agents were used, a problem occurred in that the storage stability of the resin composition was impaired.

On the other hand, it is known that a cyanate compound having a thermosetting cyanate group provides a cured product with excellent electrical properties. However, the reaction in which a cyanate group forms an S-triazine ring by thermal curing requires a relatively long curing time at a high temperature, for example, 120 minutes or more at 230°C, so it is manufactured using the build-up method described above. It was unsuitable as an organic insulating resin for multilayer printed wiring boards.

As a method of lowering the curing temperature of a cyanate compound, a method of using a cyanate compound and an epoxy resin together and curing the curing using a curing catalyst is known (for example, refer to Patent Documents 1 and 2).

In addition, the build-up layer is required to have a low thermal expansion coefficient (low CTE) due to the demand for processing dimensional stability and reduction of warpage after semiconductor packaging, and efforts are being made to reduce CTE (for example, patent documents 3 to 5). The most mainstream method is to reduce the CTE of the build-up layer by making the silica filler more dense (for example, 40% by mass or more of the build-up layer is made of silica filler).

Japanese Patent Publication No. 2013-40298 Japanese Patent Publication No. 2010-90237 Japanese Patent Publication No. 2006-527920 Japanese Patent Publication No. 2007-87982 Japanese Patent Publication No. 2009-280758

(1) When the silica filler is highly charged in order to achieve low CTE of the build-up layer, it tends to become difficult to bury the unevenness of the wiring pattern of the inner layer circuit due to the build-up material. In addition, there is a demand for filling inner layer circuits such as through holes with build-up materials so that the irregularities are small. If the silica filler is highly charged in order to achieve low CTE of the build-up material, it tends to become difficult to meet these requirements.

The first invention was made to solve this problem, and its purpose is to provide an adhesive film for a multilayer printed wiring board that has excellent embedding properties of irregularities even when the silica filler is highly filled.

(2) Additionally, in order to manufacture a multilayer printed wiring board with high yield, it is necessary to secure the adhesive strength between the interlayer insulating layer formed by thermosetting and the conductor layer formed by the above-described plating method. In addition, in order to increase the density of wiring as described above, the surface roughness of the interlayer insulating layer formed by thermal curing needs to be small.

However, as the surface roughness of the interlayer insulating layer decreases, it becomes difficult to secure the adhesive strength of the conductor layer by the so-called "anchor effect", so the adhesive strength between the interlayer insulating layer and the conductor layer tends to decrease. In addition, the interlayer insulating layer formed using a resin composition containing a cyanate compound and an epoxy resin disclosed in Patent Documents 1 and 2 is suitable for plating because the amount of functional groups having high polarity such as the above-mentioned hydroxy groups is reduced. This tends to make it difficult to secure the adhesive strength of the formed conductor layer.

In addition, the material forming the interlayer insulating layer has low thermal expansion properties and low dielectric loss tangent, and in addition, the smear (resin residue) generated when forming via holes with a laser, etc. can be easily removed by later desmear treatment. (Excellent smear removal properties) are required.

The second invention was made to solve the above problems, and the problems are (1) and (2) below.

(1) A resin composition that yields an interlayer insulating layer with excellent electrical properties, small surface roughness, and excellent adhesive strength of a conductor layer formed by a plating method, and excellent storage stability, and a resin film for an interlayer insulating layer using the resin composition. , providing multilayer printed wiring boards and semiconductor packages.

(2) To provide a resin composition that has excellent low thermal expansion properties, electrical properties, and smear removability to a high degree, and resin films for interlayer insulating layers, multilayer printed wiring boards, and semiconductor packages using the resin composition.

(1) As a result of extensive research in order to solve the first problem, the present inventors have achieved the first problem by using a resin composition containing a specific novolak-type phenol resin, a specific epoxy resin, and a specific inorganic filler. It was discovered that the problem could be solved, and the present invention was completed. That is, the first invention provides the following adhesive film.

(A) a novolak-type phenolic resin having a dispersion ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 1.05 to 1.8, and (B) an epoxy resin represented by the following general formula (1): and (C) a resin composition layer formed by forming a resin composition containing an inorganic filler on a support film, wherein the average particle size of the (C) inorganic filler in the resin composition layer is 0.1 μm or more, and (C) inorganic An adhesive film for a multilayer printed wiring board, wherein the filler content is 20 to 95% by mass based on the resin solid content.

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

(2) As a result of intensive research, the present inventors have discovered that the above-mentioned problems can be solved by the following present invention. That is, the second invention provides the following [1] to [39].

[1] A resin composition (1) containing (a1) cyanate resin, (b1) epoxy resin, (c1) inorganic filler, and (d1) polyamide resin.

[2] The resin composition (1) according to [1] above, wherein the mass ratio [(a1)/(b1)] of the (a1) cyanate resin and (b1) epoxy resin is 0.2 to 2.5.

[3] (a1) The resin composition (1) according to [1] or [2] above, wherein the cyanate resin is a prepolymer of a dicyanate compound having two cyanate groups in one molecule.

[4] (d1) Of the above [1] to [3], wherein the polyamide resin has a number average molecular weight of 20,000 to 30,000, a weight average molecular weight of 100,000 to 140,000, and is a rubber-modified polyamide resin having an amino group at the terminal. The resin composition (1) according to any one.

[5] (d1) The resin composition (1) according to any one of [1] to [4] above, wherein the polyamide resin contains a polybutadiene skeleton.

[6] (d1) The resin composition (1) according to any one of [1] to [5] above, wherein the polyamide resin content is 1 to 20 parts by mass based on 100 parts by mass in terms of solid content of the resin composition (1).

[7] (c1) The resin composition (1) according to any one of [1] to [6] above, wherein the specific surface area of the inorganic filler is 20 m 2 /g or more.

[8] (c1) The resin composition (1) according to any one of [1] to [7] above, wherein the content of the inorganic filler is 3 to 50 parts by mass based on 100 parts by mass in terms of solid content of the resin composition (1).

[9] (e1) The resin composition (1) according to any one of [1] to [8] above, further comprising a phenoxy resin.

[10] (e1) The resin composition (1) according to [9], wherein the phenoxy resin is a phenoxy resin containing an alicyclic structure.

[11] One member selected from the group consisting of (a2) cyanate resin, (b2) epoxy resin, and (c2) inorganic filler, (e2) phenoxy resin, (f2) curing accelerator, and (g2) epoxy resin curing agent. A resin composition (2) containing the above.

[12] The resin composition (2) according to [11] above, wherein the mass ratio [(a2)/(b2)] of the (a2) cyanate resin and (b2) epoxy resin is 0.1 to 3.

[13] (a2) The resin composition (2) according to [11] or [12] above, wherein the cyanate resin is a prepolymer of a dicyanate compound having two cyanate groups in one molecule.

[14] (c2) The resin composition (2) according to any one of [11] to [13] above, wherein the inorganic filler is silica.

[15] The resin composition (2) according to [14], wherein the silica is spherical silica.

[16] (c2) The resin composition (2) according to any one of [11] to [15] above, wherein the inorganic filler has a volume average particle size of 0.05 to 10 μm.

[17] (c2) [11] to [16] above, wherein the inorganic filler is surface treated with at least one surface treatment agent selected from the group consisting of a vinyl silane coupling agent, an epoxy silane coupling agent, and an amino silane coupling agent. The resin composition (2) according to any one of the above.

[18] (c2) The inorganic filler according to any one of [11] to [17] above, wherein the inorganic filler is surface treated with at least one surface treatment agent selected from the group consisting of a vinyl silane coupling agent and an epoxy silane coupling agent. Resin composition (2).

[19] (c2) The resin composition (2) according to [18] above, wherein the inorganic filler contains silica surface-treated with an epoxysilane coupling agent and silica surface-treated with a vinylsilane coupling agent.

[20] (c2) Any one of the above [11] to [19], wherein the content of the inorganic filler is 50 to 500 parts by mass based on 100 parts by mass converted to solid content of the resin composition (2) excluding the inorganic filler (c2). The described resin composition (2).

[21] (e2) The resin composition (2) according to any one of [11] to [20] above, containing a phenoxy resin.

[22] (e2) The resin composition (2) according to [21] above, wherein the phenoxy resin is a phenoxy resin containing an alicyclic structure.

[23] The resin composition according to [22], wherein the phenoxy resin containing the alicyclic structure contains at least one selected from a terpene structure and a trimethylcyclohexane structure, and has a weight average molecular weight of 2,000 to 100,000. (2).

[24] (f2) The resin composition (2) according to any one of [11] to [23] above, containing a curing accelerator.

[25] (f2) The resin composition (2) according to [24] above, wherein the curing accelerator is at least one selected from the group consisting of organometallic salts, imidazole compounds, phosphorus-based curing accelerators, and amine-based curing accelerators.

[26] (f2) The resin composition (2) according to [25] above, wherein the curing accelerator is a phosphorus-based curing accelerator.

[27] The resin composition (2) according to [26], wherein the phosphorus-based curing accelerator is an addition reaction product of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound.

[28] The addition reaction product of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to the phosphorus atom is a phosphine compound represented by the following general formula (f-1) and a phosphine compound represented by the following general formula (f-2) The resin composition (2) according to [27] above, which is an addition reaction product of a quinone compound.

(In general formula (f-1), R ^f1 represents an alkyl group having 1 to 12 carbon atoms, and R ^f2 and R ^f3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. General formula (f- 2), R ^f4 to R ^f6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^f4 and R ^f5 may be bonded to each other to form a cyclic structure.)

[29] The resin composition (2) according to any one of [26] to [28], wherein the content of the phosphorus-based curing accelerator is 0.01 to 0.5 parts by mass based on 100 parts by mass in terms of solid content of the resin composition (2).

[30] (g2) The resin composition (2) according to any one of [11] to [29] above, containing an epoxy resin curing agent.

[31] (g2) The resin composition (2) according to [30] above, containing an active ester curing agent as an epoxy resin curing agent.

[32] (g2) The resin composition (2) according to [30] or [31] above, containing dicyandiamide as an epoxy resin curing agent.

[33] Additionally, (h2) the resin composition (2) according to any one of [11] to [32] above, containing a resin having a siloxane skeleton.

[34] Additionally, (i2) the resin composition (2) according to any one of [11] to [33] above, containing a phenol compound.

[35] A resin film for an interlayer insulating layer having a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order,

A resin film for an interlayer insulating layer, wherein the adhesion auxiliary layer is a layer containing the resin composition (1) according to any one of [1] to [10].

[36] It is a resin film for an interlayer insulating layer having a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order,

A resin film for an interlayer insulating layer, wherein the resin composition layer for an interlayer insulating layer is a layer containing the resin composition (2) according to any one of [11] to [34] above.

[37] It is a resin film for an interlayer insulating layer having a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order,

The adhesion auxiliary layer is a layer containing the resin composition (1) according to any one of [1] to [10],

A resin film for an interlayer insulating layer, wherein the resin composition layer for an interlayer insulating layer is a layer containing the resin composition (2) according to any one of [11] to [34] above.

[38] At least one resin composition selected from the group consisting of the resin composition (1) according to any one of [1] to [10] above and the resin composition (2) according to any one of [11] to [34] above. A multilayer printed wiring board containing a cured product.

[39] A semiconductor package using the multilayer printed wiring board described in [38] above.

[2] According to the second invention,

(1) A resin composition (1) having excellent electrical properties, small surface roughness, excellent adhesive strength of a conductor layer formed by a plating method, and excellent storage stability, and

(2) A resin composition that has excellent low thermal expansion properties, electrical properties, and smear removability to a high degree,

And resin films for interlayer insulating layers, multilayer printed wiring boards, and semiconductor packages using these resin compositions can be provided.

[1] First invention

The adhesive film for a multilayer printed wiring board of the present invention is (A) a novolak-type phenolic resin (hereinafter simply, (also referred to as “(A) novolak-type phenol resin”), (B) an epoxy resin represented by the above general formula (1) (hereinafter also simply referred to as “(B) epoxy resin”), and (C) an inorganic filler. It has a resin composition layer formed by forming a resin composition containing (hereinafter also referred to as "resin composition for adhesive film") on a support film, and the average particle diameter of the (C) inorganic filler in the resin composition layer is 0.1 ㎛ or more. , (C) It is an adhesive film for a multilayer printed wiring board in which the content of the inorganic filler is 20 to 95% by mass based on the resin solid content.

[Resin composition for adhesive film]

The resin composition for an adhesive film contains (A) a novolak-type phenol resin, (B) an epoxy resin, and (C) an inorganic filler. Hereinafter, each of these components will be explained.

<(A) Novolac type phenol resin>

(A) The novolak-type phenol resin is used as a curing agent for epoxy resin, and has a dispersion ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the range of 1.05 to 1.8.

Such (A) novolak-type phenol resin can be manufactured, for example, by the manufacturing method described in Japanese Patent No. 4283773.

That is, a phenolic compound and an aldehyde compound are used as raw materials, a phosphoric acid compound is used as an acid catalyst, and a non-reactive oxygen-containing organic solvent is used as a reaction auxiliary solvent, and the two-layer separation state formed by these is subjected to, for example, mechanical stirring, ultrasonic waves, etc. By stirring and mixing the two layers (organic phase and aqueous phase) to form a cloudy heterogeneous reaction system (phase separation reaction) mixed with each other, the reaction between the phenol compound and the aldehyde compound can proceed to synthesize the condensate (resin).

Next, for example, a non-aqueous organic solvent (e.g., methyl ethyl ketone, methyl isobutyl ketone, etc.) is added and mixed to dissolve the above-described condensate, and the stirring and mixing is stopped and left to stand to form an organic phase (organic solvent phase). ) and an aqueous phase (phosphoric acid aqueous solution phase), and the aqueous phase is removed to recover the organic phase, while the organic phase is washed with hot water and/or neutralized, and the organic solvent is distilled and recovered to produce (A) a novolak-type phenolic resin. can do.

Since the method for producing the novolak-type phenol resin uses a phase separation reaction, stirring efficiency is very important, and it is desirable in terms of reaction efficiency to increase the surface area of the interface as much as possible by miniaturizing both phases in the reaction system, This promotes the conversion of the phenol compound into the resin.

Phenolic compounds that can be used as raw materials include, for example, phenol, orthocresol, metacresol, para-cresol, xylenol, bisphenol compounds, and ortho compounds having a hydrocarbon group of 3 or more carbon atoms at the ortho position, preferably 3 to 10 carbon atoms. Substituted phenol compounds, para-substituted phenol compounds having a hydrocarbon group in the para position of 3 or more carbon atoms, preferably 3 to 18 carbon atoms, etc. can be mentioned. These may be used individually or in mixture of two or more types.

Here, examples of bisphenol compounds include bisphenol A, bisphenol F, bis(2-methylphenol) A, bis(2-methylphenol) F, bisphenol S, bisphenol E, and bisphenol Z.

Examples of ortho-substituted phenol compounds include 2-propylphenol, 2-isopropylphenol, 2-sec-butylphenol, 2-tert-butylphenol, 2-phenylphenol, 2-cyclohexylphenol, and 2-nonylphenol. , 2-naphthylphenol, etc.

Examples of para-substituted phenol compounds include 4-propylphenol, 4-isopropylphenol, 4-sec-butylphenol, 4-tert-butylphenol, 4-phenylphenol, 4-cyclohexylphenol, and 4-nonylphenol. , 4-naphthylphenol, 4-dodecylphenol, 4-octadecylphenol, etc.

Examples of aldehyde compounds that can be used as raw materials include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, paraldehyde, and propionaldehyde. Among these, paraformaldehyde is preferable from the viewpoint of reaction speed. These may be used individually or in mixture of two or more types.

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

The phosphoric acid compound used as the acid catalyst plays an important role in forming a site for a phase separation reaction between the phenol compound and the phenol compound in the presence of water. As the phosphoric acid compound, for example, an aqueous solution type such as 89 mass% phosphoric acid or 75 mass% phosphoric acid can be used. Additionally, if necessary, for example, polyphosphoric acid, phosphoric acid anhydride, etc. may be used.

From the viewpoint of controlling the phase separation effect, the content of the phosphoric acid compound is, for example, 5 parts by mass or more, preferably 25 parts by mass or more, and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the phenol compound. In addition, when using 70 parts by mass or more of a phosphoric acid compound, it is preferable to suppress heat generation at the initial stage of the reaction and ensure safety by dividing it into the reaction system.

A non-reactive oxygen-containing organic solvent as a reaction auxiliary solvent plays a very important role in promoting the phase separation reaction. As the reaction auxiliary solvent, it is preferable to use at least one compound selected from the group consisting of alcohol compounds, polyhydric alcohol-based ethers, cyclic ether compounds, polyhydric alcohol-based esters, ketone compounds, and sulfoxide compounds.

Examples of alcohol compounds include monohydric alcohols such as methanol, ethanol, and propanol, butanediol, pentanediol, hexanediol, ethylene glycol, propylene glycol, trimethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and triethylene glycol. Examples include dihydric alcohols such as propylene glycol and polyethylene glycol, and trihydric alcohols such as glycerin.

Examples of polyhydric alcohol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, and ethylene glycol ethylmethyl ether. , ethylene glycol glycol ether, etc.

Examples of cyclic ether compounds include 1,3-dioxane and 1,4-dioxane, and examples of polyhydric alcohol-based esters include glycol ester compounds such as ethylene glycol acetate. there is. Examples of ketone compounds include acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), and methyl isobutyl ketone. Examples of sulfoxide compounds include dimethyl sulfoxide and diethyl sulfoxide. etc. can be mentioned.

Among these, ethylene glycol monomethyl ether, polyethylene glycol, and 1,4-dioxane are preferable.

The reaction auxiliary solvent is not limited to the above examples, and may be a solid as long as it has the above-mentioned characteristics and exhibits a liquid state during the reaction, and may be used individually or in a mixture of two or more types.

The compounding amount of the reaction auxiliary solvent is not particularly limited, but is, for example, 5 parts by mass or more, preferably 10 to 200 parts by mass, per 100 parts by mass of the phenol compound.

By additionally using a surfactant during the heterogeneous reaction process, it is possible to accelerate the phase separation reaction and shorten the reaction time, which can also contribute to improving yield.

Surfactants include, for example, soap, α-olefin sulfonate, alkylbenzene sulfonate and its salts, alkyl sulfuric acid ester salts, alkyl ether sulfuric acid ester salts, phenyl ether ester salts, polyoxyethylene alkyl ether sulfuric acid ester salts, and ether sulfonate salts. , anionic surfactants such as ether carboxylates; Polyoxyethylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyethylene styrenated phenol ether, polyoxyethylene alkylamino ether, polyethylene glycol aliphatic ester, aliphatic monoglyceride, sorbitan aliphatic ester, pentaerythritol aliphatic ester, poly Nonionic surfactants such as oxyethylene polypropylene glycol and aliphatic alkylolamide; Cationic surfactants such as monoalkylammonium chloride, dialkylammonium chloride, and amine acid salt compounds can be mentioned.

The mixing amount of the surfactant is not particularly limited, but is, for example, 0.5 parts by mass or more, preferably 1 to 10 parts by mass, per 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 is generally 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 maintained well.

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

Additionally, the reaction environment is usually normal pressure, but from the viewpoint of maintaining the heterogeneous reaction that is a feature of the present invention, the reaction may be performed under increased or reduced pressure. For example, under pressurization of 0.03 to 1.50 MPa, the reaction rate can be increased, and it also becomes possible to use a low boiling point solvent such as methanol as a reaction auxiliary solvent.

By the method for producing the (A) novolak-type phenol resin, a novolak-type phenol resin having a dispersion ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 1.05 to 1.8 can be produced. there is.

Although it varies depending on the type of phenol compound, depending on the range of the compounding molar ratio (F/P) of the aldehyde compound (F) and the phenol compound (P), for example, (A) novolac type phenol resin as shown below can be obtained. Lose.

When the compounding molar ratio (F/P) is in the range of 0.33 or more and less than 0.80, the content of the monomer component of the phenol compound is preferably, for example, 3% by mass or less as measured by the area method of gel permeation chromatography (GPC). It is 1% by mass or less, and the content of the dimer component of the phenolic compound is, for example, 5 to 95% by mass, preferably 10 to 95% by mass, and the weight average molecular weight (Mw) by GPC measurement and A novolak-type phenol resin having a dispersion ratio (Mw/Mn) of number average molecular weight (Mn) of 1.05 to 1.8, preferably 1.1 to 1.7, can be produced in high yield.

(A) As the novolak-type phenolic resin, commercially available products can be used, for example, “PAPS-PN2” (manufactured by Asahi Yukizai Kogyo Co., Ltd., brand name), “PAPS-PN3” (manufactured by Asahi Yukizai Kogyo Co., Ltd., brand name) Kaisha product, brand name), etc. can be mentioned.

The resin composition for adhesive film may be used in combination with an epoxy resin curing agent (hereinafter also simply referred to as “epoxy resin curing agent”) other than (A) novolak-type phenol resin, within a range that does not impair the effect of the present invention.

Examples of the epoxy resin curing agent include various phenol resin compounds other than (A) novolak-type phenol resin, acid anhydride compounds, amine compounds, and hydrazide compounds. Examples of phenol resin compounds include novolak-type phenol resins other than (A) novolak-type phenol resin, resol-type phenol resins, etc., and examples of acid anhydride compounds include phthalic anhydride and benzophenone tetra. Carboxylic dianhydride, methyl hymic acid, etc. can be mentioned. Additionally, examples of amine compounds include dicyandiamide, diaminodiphenylmethane, and guanylurea.

Among these epoxy resin curing agents, from the viewpoint of improving reliability, novolak-type phenol resins other than (A) novolak-type phenol resin are preferable.

Moreover, from the viewpoint of improving the peeling strength of metal foil and the peeling strength of electroless plating after chemical roughening, triazine ring-containing novolak-type phenol resin and dicyandiamide are preferable.

(A) Novolak-type phenol resins other than the novolak-type phenol resin may be commercially available, for example, phenol novolak resins such as “TD2090” (DIC Co., Ltd., brand name), “KA-1165” Cresol novolac resins such as "(manufactured by DIC Corporation, brand name)." In addition, commercially available products of triazine ring-containing novolak-type phenol resin include, for example, “Phenolite LA-1356” (manufactured by DIC Corporation, brand name) and “Phenolite LA7050 Series” (manufactured by DIC Corporation, brand name). and the like, and commercially available products of triazine-containing cresol novolak resin include, for example, “Phenolite LA-3018” (brand name, manufactured by DIC Corporation).

<(B) Epoxy resin>

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

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

(B) As the epoxy resin, a commercially available product may be used. Commercially available epoxy resins (B) include, for example, “NC-3000” (an epoxy resin in which p in formula (1) is 1.7) and “NC-3000-H” (p in formula (1)). epoxy resins with a value of 2.8 (all manufactured by Nippon Kayaku Co., Ltd., brand names), etc.

The resin composition for adhesive film may contain an epoxy resin other than the epoxy resin (B), a polymer-type epoxy resin such as a phenoxy resin, etc., as long as it does not impair the effect of the present invention.

<Curing accelerator>

The resin composition for an adhesive film may contain a curing accelerator from the viewpoint of speeding up the reaction between (A) the novolak-type phenolic resin and (B) the epoxy resin. Examples of the curing accelerator include imidazole compounds such as 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; Organic phosphorus compounds such as triphenylphosphine; Onium salts such as phosphonium borate; Amines such as 1,8-diazabicycloundecene; 3-(3,4-dichlorophenyl)-1,1-dimethylurea, etc. are mentioned. These may be used individually or in mixture of two or more types.

<(C) Inorganic filler>

The resin composition for adhesive film contains (C) an inorganic filler having an average particle diameter of 0.1 μm or more.

(C) Inorganic fillers include, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. can be mentioned. These may be used individually or in mixture of two or more types. Among these, silica is preferable from the viewpoint of lowering the thermal expansion coefficient of the interlayer insulating layer formed by curing the adhesive film.

(C) The shape of the inorganic filler is not particularly limited, but is preferably spherical from the viewpoint of making it easier to fill 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 properties, the content of the inorganic filler with an average particle diameter of less than 0.1 μm is preferably 3 vol% or less, more preferably 1 vol% or less, and even more preferably does not contain the inorganic filler with an average particle diameter of less than 0.1 μm. do. In addition, (C) the inorganic filler may be used individually, or may be used in mixture of those having different average particle sizes.

(C) Commercially available products may be used as inorganic fillers. Commercially available (C) inorganic fillers include, for example, spherical silica “SO-C1” (average particle size: 0.25 μm), “SO-C2” (average particle size: 0.5 μm), and “SO-C3” (average particle size: 0.25 μm). Particle size: 0.9 μm), “SO-C5” (average particle size: 1.6 μm), and “SO-C6” (average particle size: 2.2 μm) (all manufactured by Admatex Co., Ltd.).

(C) The inorganic filler may be one that has undergone surface treatment. For example, when silica is used as the inorganic filler (C), silane coupling agent treatment may be performed as surface treatment. Examples of silane coupling agents include aminosilane coupling agents, vinylsilane coupling agents, and epoxysilane coupling agents. Among these, silica surface-treated with an aminosilane coupling agent is preferable.

The amount of (C) inorganic filler in the resin composition for adhesive film is defined as follows. First, the resin composition to form a layer on the support film is dried at 200°C for 30 minutes, the solvent contained in the resin composition is removed, and the weight (solid content) after removing the solvent is measured. The amount of (C) inorganic filler contained in this solid content is defined as the amount of (C) inorganic filler in the resin solid content.

Additionally, as a method of measuring the (C) inorganic filler, if the amount of solid content of the (C) inorganic filler to be blended is calculated in advance, the ratio in the solid content can be easily determined. An example of calculation in the case of using the (C) inorganic filler dispersed in a solvent (hereinafter also referred to as “(C) inorganic filler dispersion”) is shown below.

The solid content of the (C) inorganic filler in the (C) inorganic filler dispersion was calculated by drying at 200°C for 30 minutes, and was found to be 70% by mass. As a result of blending a resin composition using 40 g of this (C) inorganic filler dispersion, 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 solid weight after drying was measured and found to be 60 g. Since the amount of the (C) inorganic filler contained in the solid content is 40 g

The larger the amount of the inorganic filler (C) in the resin composition for adhesive film, the more preferable it is from the viewpoint of lowering the thermal expansion coefficient of the interlayer insulating layer after heat curing, but from the viewpoint of filling the irregularities and through holes of the wiring pattern of the inner layer circuit board to be formed. There is an appropriate amount of inorganic filler. From this viewpoint, the content of the inorganic filler (C) is 20 to 95% by mass, preferably 30 to 90% by mass, and more preferably 50 to 90% by mass, based on the resin solid content. (C) If the content of the inorganic filler is 20% by mass or more, the thermal expansion coefficient can be lowered, and if the content of the inorganic filler is 95% by mass or less, the embedding property can be maintained well.

<Flame retardant>

The resin composition for adhesive film may further contain a flame retardant.

The flame retardant is not particularly limited, but examples include inorganic flame retardants and resin flame retardants.

Examples of the inorganic flame retardant include aluminum hydroxide and magnesium hydroxide, which are exemplified as (C) inorganic fillers.

The resin flame retardant may be a halogen-based resin or a non-halogen-based resin, but it is preferable to use a non-halogen-based resin out of consideration for environmental impact. The resin flame retardant may be blended as a filler or may have a functional group that reacts with the thermosetting resin.

The resin flame retardant can be a commercially available product. Commercially available resin flame retardants mixed as fillers include, for example, "PX-200" (trade name, manufactured by Daihachi Chemical Industries, Ltd.), an aromatic phosphoric acid ester-based flame retardant, and "Exolit OP 930" (Clariant), which is a polyphosphate compound. Product made by Japan Corporation, brand name), etc. can be mentioned.

Commercially available resin flame retardants having functional groups that react with thermosetting resins include epoxy-based phosphorus-containing flame retardants, phenol-based phosphorus-containing flame retardants, and the like. Examples of the epoxy-based phosphorus-containing flame retardant include “FX-305” (manufactured by Nippon-based Sumikin Chemical Co., Ltd., brand name), and examples of the phenol-based phosphorus-containing flame retardant include “HCA- HQ” (manufactured by Sanko Corporation, brand name), “XZ92741” (manufactured by Dow Chemical Company, brand name), etc. These may be used individually or in mixture of two or more types.

<Solvent>

The resin composition for adhesive film preferably contains a solvent from the viewpoint of efficient layer formation. Examples of solvents include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Acetic acid ester compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; Carbitol compounds such as cellosolve, methylcarbitol, and butylcarbitol; Aromatic hydrocarbon compounds such as toluene and xylene; Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, etc. are mentioned. These may be used individually or in mixture of two or more types.

<Residual solvent amount>

The amount of residual solvent in the adhesive film of the present invention varies depending on the material being handled, but is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 2 to 10% by mass. do. If the residual solvent amount is 1% by mass or more, the handleability of the adhesive film improves, and, for example, the occurrence of powder dropping and cracking when cutting with a cutter can be suppressed. On the other hand, if it is 20 mass % or less, tackiness is suppressed and winding and unwinding of the film becomes easy. In addition, in order to enable unwinding, a protective film is often provided on the varnish-coated surface of the adhesive film after drying. However, if the residual solvent amount is 20% by mass or less, peeling between the protective film and the adhesive film of the present invention becomes easy.

In addition, since the residual solvent is removed by drying and heat curing in the process of manufacturing a multilayer printed wiring board, it is preferable to have less residual solvent from the viewpoint of environmental impact, and to reduce the change in film thickness before and after drying and heat curing. For this reason, it is preferable to have less.

In addition, in the production of the adhesive film of the present invention, it is preferable to determine drying conditions so that the target residual solvent amount is achieved. Since drying conditions differ depending on the type of solvent contained in the above-mentioned resin composition, the amount of solvent, etc., it is preferable to determine the conditions after presenting the conditions in advance with each coating device.

Here, the amount of residual solvent in the present invention is the ratio (mass %) of the solvent contained in the resin composition layer of the support film, and can be defined as follows.

First, the weight (W _a ) of the support film is measured, and the weight (W _b ) after forming the resin composition layer thereon is measured. Thereafter, the support film and the resin composition layer formed thereon are left in a dryer at 200°C for 10 minutes, and the weight (W _c ) after drying is measured. It can be calculated by the following formula using the obtained weights (W _a ) to (W _c ).

Ratio of solvent (mass%) = (1-((W _c )-(W _a ))/((W _b )-(W _a )))×100

<Other ingredients>

The adhesive film of the present invention may contain other components as long as they do not impair the effects of the present invention. Other ingredients include, for example, thickeners such as orbene and bentone; Ultraviolet absorbers such as thiazole-based and triazole-based; Adhesion imparting agents such as silane coupling agents; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black; Arbitrary resin components other than those mentioned above can be mentioned.

[Support film]

The support film in the present invention serves as a support when manufacturing the adhesive film of the present invention, and is usually finally peeled or removed when manufacturing a multilayer printed wiring board.

The support film is not particularly limited, but examples include organic resin films, metal foils, and release papers.

Materials for 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; Polycarbonate, polyimide, etc. can be mentioned. Among these, PET is preferable from the viewpoint of price and handleability.

Examples of metal foil include copper foil and aluminum foil. When copper foil is used for the support, a circuit can also be formed using the copper foil as a conductor layer. In this case, rolled copper, electrolytic copper foil, etc. can be used as the copper foil. In addition, the thickness of the copper foil is not particularly limited, but for example, one having a thickness of 2 to 36 μm can be used. When using thin copper foil, you may use copper foil with a carrier from the viewpoint of improving workability.

These support films and the protective film described later may be subjected to surface treatment such as release treatment, plasma treatment, or corona treatment. Examples of the mold release treatment include mold release treatment using a silicone resin-based mold release agent, an alkyd resin-based mold release agent, and a fluororesin-based mold release agent.

The thickness of the support film is not particularly limited, but from the viewpoint of handling, it is preferably 10 to 120 μm, more preferably 15 to 80 μm, and even more preferably 15 to 70 μm.

The support film does not need to be a single component as described above, and may be formed of multiple layers (two or more layers) of different materials.

As an example in which the support film has a two-layer structure, for example, as the first layer support film, the support film mentioned above is used, and as the second layer, a layer formed of an epoxy resin, an epoxy resin curing agent, a filler, etc. It can be mentioned that it has . The material used in the second layer can also be a material derived from the material used in the adhesive film of the present invention.

The layer formed on the first layer support film (after the second layer, there may be a plurality of two or more layers) is a layer produced with the intention of providing a function, for example, for the purpose of improving adhesion to plated copper, etc. It can be used as .

The method of forming the second layer is not particularly limited, but includes, for example, a method of applying and drying a varnish obtained by dissolving and dispersing each material in a solvent onto the first layer support film.

When the support film is formed in multiple layers, the thickness of the first layer support film is preferably 10 to 100 μm, more preferably 10 to 60 μm, and still more preferably 13 to 50 μm.

The thickness of the layer formed on the first-layer support film (second and subsequent layers may be two or more layers) is preferably 1 to 20 μm. If it is 1 μm or more, the intended function can be performed, and if it is 20 μm or less, it is excellent in economic efficiency as a support film.

When the support film is formed of multiple layers, when peeling the support film, the layer formed and left on the multilayer printed wiring board side together with the adhesive film of the present invention (may be two or more layers) and the layer to be peeled off or removed (2) It may be separated into layers (may be more than one layer).

[Protective Film]

The adhesive film of the present invention may have a protective film. The protective film is installed on the side opposite to the side on which the support of the adhesive film is installed, and is used for the purpose of preventing adhesion of foreign substances, etc. to the adhesive film and occurrence of scratches. The protective film is peeled off before laminating the adhesive film of the present invention on a circuit board, etc. by laminating, heat pressing, etc.

The protective film is not particularly limited, but the same material as the support film can be used. The thickness of the protective film is not particularly limited, but for example, one having a thickness of 1 to 40 μm can be used.

[Method for manufacturing adhesive film]

The adhesive film of the present invention can be manufactured by applying and drying the resin composition for adhesive film on a support film. The obtained adhesive film can be wound into a roll, preserved and stored. More specifically, for example, after dissolving each of the above-mentioned resin components in the above-mentioned organic solvent, (C) mixing an inorganic filler, etc. to prepare a resin composition for an adhesive film, the varnish is applied on the support film, heated, It can be manufactured by drying the organic solvent using hot air spraying or the like and forming a resin composition layer on the support film.

In addition, 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 (B-staged) state.

The method of applying the varnish to the support film is not particularly limited, but for example, a method of applying the varnish using a known coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, or die coater is applied. can do. The coating device may be appropriately selected according to the target film thickness.

[2] Second invention

Next, the resin compositions (1) and (2), the resin film for interlayer insulating layer, the multilayer printed wiring board, and the semiconductor package according to the second invention are explained.

In addition, hereinafter, when simply referred to as “resin composition”, it refers to both the resin composition (1) and the resin composition (2).

[Resin composition (1)]

The resin composition (1) contains (a1) cyanate resin, (b1) epoxy resin, (c1) inorganic filler, and (d1) polyamide resin.

<(a1) cyanate resin>

(a1) As a cyanate resin, a cyanate resin having two or more cyanate groups per molecule is preferably used, for example.

(a1) Cyanate resin may be used individually by 1 type, or may use 2 or more types together.

(a1) Cyanate resins include 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2, Bisphenol type cyanate resins such as 2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane; Dicyclopentadiene type cyanate resins such as cyanate ester compounds of phenol addition dicyclopentadiene polymers; Novolak-type cyanate resins such as phenol novolak-type cyanate ester compounds and cresol novolak-type cyanate ester compounds; α,α'-bis(4-cyanatophenyl)-m-diisopropylbenzene; Prepolymers of these cyanate resins (hereinafter also referred to as “cyanate prepolymers”), etc. can be mentioned.

Among these, from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, cyanate resin represented by the following general formula (a-1), and the following general formula (a-2) ) Cyanate resins represented by and their prepolymers are preferable, and cyanate resins represented by the following general formula (a-1) and prepolymers of these cyanate resins are more preferable.

In general formula (a-1), R ^a1 is an alkylene group having 1 to 3 carbon atoms which may be substituted with a halogen atom, a sulfur atom, the following general formula (a-1') or the following formula (a-1'') Indicates the divalent group displayed. R ^a2 and R ^a3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A plurality of R ^a2 or R ^a3 may be the same or different.

In addition, in this specification, an alkylene group shall include an alkylidene group.

In general formula (a-1'), R ^a4 each independently represents an alkylene group having 1 to 3 carbon atoms.

In general formula (a-2), R ^a5 each independently represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. p represents an integer of 1 or more.

From the viewpoint of handleability, p is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.

In the general formula (a-1), the alkylene group having 1 to 3 carbon atoms represented by R ^a1 includes methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, and 2,2-propylene group. (-C(CH ₃ ) ₂ -) and the like. Among these, methylene group and 2,2-propylene group are preferable, and 2,2-propylene group is preferable from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method.

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.

In the general formula (a-1'), the alkylene group having 1 to 3 carbon atoms represented by R ^a4 includes methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, and 2,2-propylene. etc. can be mentioned.

Among these groups represented by R ^a1 , methylene group and 2,2-propylene group are preferable from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, and 2,2- A propylene group is more preferable.

In the general formula (a-1), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^a2 or R ^a3 include methyl group, ethyl group, propyl group, butyl group, etc.

In the general formula (a-2), examples of the alkyl group having 1 to 3 carbon atoms represented by R ^a5 include methyl group, ethyl group, and 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 general formula (a-2), p represents an integer of 1 or more, and is preferably 1 to 7 from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, and 1 to 4 are more preferable.

The above-mentioned cyanate prepolymer refers to a polymer in which cyanate resins form a triazine ring through a cyclization reaction, and mainly includes 3, 5, 7, 9, and 11 polymers of cyanate ester compounds. In this cyanate prepolymer, the conversion rate of cyanate groups is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 40 to 80% by mass from the viewpoint of obtaining good solubility in organic solvents. It is more preferable, and 40 to 70 mass% is particularly preferable.

Examples of the cyanate prepolymer include a prepolymer of a cyanate resin represented by the general formula (a-1), a prepolymer of a cyanate resin represented by the general formula (a-2), and the like. Among these, a prepolymer of a dicyanate compound having two cyanate groups per molecule is preferred from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, and having the general formula above A prepolymer of cyanate resin represented by (a-1) is more preferable, and is a prepolymer in which at least part of 2,2-bis(4-cyanatophenyl)propane is triazineized to form a trimer (formula (a-3) below) reference) is more preferable.

The weight average molecular weight (Mw) of the cyanate prepolymer is preferably 500 to 100,000, more preferably 600 to 50,000, more preferably 1,000 to 40,000, and especially 1,500 to 30,000 from the viewpoint of solubility in organic solvents and workability. desirable. If the weight average molecular weight of the cyanate prepolymer is 500 or more, crystallization of the cyanate prepolymer is suppressed and solubility in organic solvents tends to improve, and if it is 100,000 or less, increase in viscosity is suppressed and workability tends to be excellent. There is. Therefore, from the viewpoint of improving solubility in organic solvents, the weight average molecular weight (Mw) of the cyanate prepolymer may be 4,500 or less, or 4,000 or less, and from the viewpoint of improving workability, it may be 1,500 or more. It can be 2,000 or more.

In addition, in this specification, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a calibration curve of standard polystyrene, and in detail, the method described in the Examples. It was measured according to .

The cyanate prepolymer may be obtained by prepolymerizing the above cyanate resin in the presence of a monofunctional phenol compound. When producing a cyanate prepolymer, by blending a monofunctional phenol compound, unreacted cyanate groups in the resulting cured product can be reduced, so moisture resistance and electrical properties tend to be excellent.

Examples of the monofunctional phenol compound include alkyl group-substituted phenol compounds such as p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol; and phenolic compounds represented by the following general formula (a-4), such as p-(α-cumyl)phenol, mono-, di-, or tri-(α-methylbenzyl)phenol. These monofunctional phenol compounds may be used individually by 1 type, or may be used in combination of 2 or more types.

In general formula (a-4), R ^a and R ^b each independently represent a hydrogen atom or a methyl group, and q represents an integer of 1 to 3. When s is an integer of 2 or 3, a plurality of R ^a or R ^b may be the same or different.

The equivalent ratio (hydroxyl group/cyanate group) of the phenolic hydroxyl group of the monofunctional phenol compound and the cyanate group contained in (a1) cyanate resin is 0.01 to 0.3 from the viewpoint of dielectric properties and moisture resistance of the resulting interlayer insulating layer. is preferable, 0.01 to 0.2 is more preferable, and 0.01 to 0.15 is further preferable. If the equivalence ratio (hydroxyl group/cyanate group) is within the above range, a sufficiently low dielectric loss tangent, especially in a high frequency band, tends to be obtained, and good moisture resistance tends to be obtained.

There is no particular limitation as a method for producing the cyanate prepolymer, and a known production method can be applied.

The cyanate prepolymer can be suitably produced, for example, by reacting the dicyanate compound and the monofunctional phenol compound. By the reaction of a dicyanate compound and a monofunctional phenol compound, a compound having a group represented by -O-C(=NH)-O- (i.e., iminocarbonate) is formed, and the iminocarbonates react with each other. Alternatively, when the iminocarbonate and the dicyanate compound react, the monofunctional phenol compound is desorbed and a cyanate prepolymer having a triazine ring is obtained. In the above reaction, for example, the dicyanate compound and the monofunctional phenol compound are mixed and dissolved in the presence of a solvent such as toluene, maintained at 80 to 120° C., and, if necessary, reaction such as zinc naphthenate. This can be done by adding an accelerator.

(a1) As the cyanate resin, you may use a commercial item. Examples of commercially available (a1) cyanate resins include bisphenol-type cyanate resins, novolak-type cyanate resins, and prepolymers in which part or all of these cyanate resins are triazineized to form trimers.

Commercially available products of bisphenol A type (2,2-bis(4-hydroxyphenyl)propane type) cyanate resin include “Primaset BADCy” (manufactured by Lonza, brand name), “Arocy B-” 10” (manufactured by Huntsman, brand name). In addition, commercially available products of bisphenol E type (1,1-bis(4-hydroxyphenyl)ethane type) cyanate resin include “Arocy L10” (manufactured by Huntsman, brand name) and “Primaset.” )LECy" (manufactured by Lonza, brand name), etc., and commercially available products of 2,2'-bis(4-cyanate-3,5-methylphenyl)ethane type cyanate resin include "Primaset METHYLCy. 」(manufactured by Lonza Corporation), etc.

Commercially available products of novolak-type cyanate resin include "Primaset PT30" (manufactured by Lonza Corporation, brand name), which is a phenol novolak-type cyanate resin.

Commercially available prepolymers of cyanate resin include "Primaset BA200" (manufactured by Lonza, brand name) and "Primaset BA230S" (manufactured by Lonza, brand name), which are prepolymerized bisphenol A cyanate resins. Examples include "Primaset BA3000" and the like.

In addition, “Arocy "Primaset DT-4000" (manufactured by Lonza, brand name), "Primaset DT-7000" (manufactured by Lonza, brand name), etc. are mentioned.

The content of (a1) cyanate resin in the resin composition (1) is calculated as the solid content of the resin composition (1) from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method. Relative to 100 parts by mass, 5 to 70 parts by mass is preferable, 10 to 60 parts by mass is preferable, 15 to 50 parts by mass is more preferable, and 20 to 40 parts by mass is still more preferable.

Here, “solid content conversion” in the present invention means based only on the non-volatile content excluding volatile components such as organic solvents. That is, 100 parts by mass in terms of solid content means 100 parts by mass of non-volatile content.

<(b1) epoxy resin>

(b1) Preferred examples of the epoxy resin include epoxy resins having two or more epoxy groups in one molecule.

(b1) Epoxy resins may be used individually, or two or more types may be used together.

(b1) Examples of the epoxy resin include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; Phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol A novolak-type epoxy resin, bisphenol S novolak-type epoxy resin, dicyclopentadiene novolak-type epoxy resin, anthracene novolak-type epoxy resin, aralkylnovolak-type epoxy resin Novolak-type epoxy resins such as rockfish-type epoxy resins and naphthol novolak-type epoxy resins; Biphenol type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type epoxy resin, tert-butyl-catechol type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, etc. can be mentioned.

Among these, from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, aralkyl novolak-type epoxy resin is preferable, and aralkyl novolak-type epoxy resin having a biphenyl skeleton is preferred. Resins are more preferred. The aralkyl novolak-type epoxy resin having a biphenyl skeleton refers to an aralkyl novolak-type epoxy resin containing an aromatic ring of a biphenyl derivative in the molecule, and has a structural unit represented by the general formula (b-1) below: and epoxy resins contained therein.

In general formula (b-1), R ^b1 represents a hydrogen atom or a methyl group.

The content of the structural unit represented by the general formula (b-1) in the epoxy resin containing the structural unit represented by the general formula (b-1) has a low surface roughness and is effective in adhesion of the conductor layer formed by the plating method. From the viewpoint of obtaining an interlayer insulating layer with excellent strength, 50 to 100 mass% is preferable, 70 to 100 mass% is more preferable, and 80 to 100 mass% is still more preferable.

Examples of the epoxy resin containing the structural unit represented by the general formula (b-1) include an epoxy resin represented by the following general formula (b-2).

In general formula (b-2), R ^b1 is as described above, and m represents an integer of 1 to 20. A plurality of R ^b1 may be the same or different.

(b1) As the epoxy resin, a commercially available product may be used. Commercially available (b1) epoxy resins include "NC-3000-H", "NC-3000-L", "NC-3100", and "NC-3000" (above, manufactured by Nippon Kayaku Co., Ltd., brand name, ratio) Aralkyl novolak-type epoxy resin having a phenyl skeleton), “NC-2000-L” (Nippon Kayaku Co., Ltd., brand name, phenol aralkyl-type epoxy resin) “NC-7000-L” (Nippon Kayaku Co., Ltd.) Shiki Kaisha Co., Ltd., brand name, naphthol novolak-type epoxy resin), “N673” (DIC Co., Ltd., brand name, cresol novolac-type epoxy resin), “N740”, “N770”, “N775”, “N730-A” ” (above, manufactured by DIC Corporation, brand name, phenol novolac type epoxy resin), “Ep828” (manufactured by Mitsubishi Chemical Corporation, brand name, bisphenol A type liquid epoxy resin), “840S” (DIC Corporation) Kaisha product, brand name, liquid bisphenol A type epoxy resin), etc. are mentioned.

(b1) The epoxy equivalent weight of the epoxy resin is preferably 150 to 500 g/eq, from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, and 150 to 400 g/eq. It is more preferable, and 200 to 300 g/eq is even more preferable.

Here, the epoxy equivalent is the mass (g/eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K 7236. Specifically, using an automatic titrator "GT-200 type" manufactured by Mitsubishi Chemical Analytech Co., Ltd., 2 g of epoxy resin was weighed in a 200 ml beaker, 90 ml of MEK was added dropwise, and after dissolution in an ultrasonic cleaner, 10 ml of glacial acetic acid was added. and 1.5 g of cetyltrimethylammonium bromide, and titrated with a 0.1 mol/L perchloric acid/acetic acid solution.

The content of the epoxy resin (b1) in the resin composition (1) is 100 in terms of solid content of the resin composition (1) from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method. 20 to 80 parts by mass is preferable, 30 to 70 parts by mass is more preferable, 40 to 65 parts by mass is still more preferable, and 35 to 60 parts by mass is particularly preferable.

In the resin composition (1), the mass ratio [(a1)/(b1)] of the (a1) cyanate resin and (b1) epoxy resin is such that the surface roughness is small and the adhesive strength of the conductor layer formed by the plating method is excellent. From the viewpoint of obtaining an interlayer insulating layer, 0.2 to 2.5 is preferable, 0.3 to 2 is more preferable, and 0.5 to 1.25 is still more preferable. If the mass ratio [(a1)/(b1)] is 0.2 or more, the amount of unreacted epoxy groups in the resulting interlayer insulating layer tends to be reduced, and if it is 2.5 or less, the amount of (a1) cyanate resin blended does not become too large. Therefore, there is a tendency to suppress the increase in curing temperature.

<(c1) Inorganic filler>

The resin composition (1) also contains (c1) an inorganic filler.

(c1) The inorganic filler is important from the viewpoint of preventing scattering of the resin when laser processing the interlayer insulating layer formed by thermosetting the resin composition (1) and making it possible to adjust the shape for laser processing. In addition, it is important to form an appropriate roughened surface when roughening the surface of the interlayer insulating layer with an oxidizing agent and enable the formation of a conductor layer with excellent adhesive strength by plating, and it is preferable to select from that viewpoint.

(c1) Inorganic fillers may be used individually or in combination of two or more types.

(c1) Inorganic fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, Examples include calcium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica is preferable from the viewpoint of thermal expansion coefficient, varnish handleability, and insulation reliability.

Examples of silica include precipitated silica with a high moisture content produced by a wet process, dry-processed silica containing little bound water, etc. produced by a dry process, and dry-processed silica, depending on differences in production methods, such as crushed silica and fumed silica. Rica, fused silica (fused spherical silica), etc. are mentioned.

(c1) The inorganic filler preferably has a small particle diameter from the viewpoint of forming fine wiring. Moreover, from the same viewpoint, the specific surface area of the (c1) inorganic filler is preferably 20 m 2 /g or more, more preferably 60 to 200 m 2 /g, and still more preferably 90 to 130 m 2 /g.

The specific surface area can be obtained by the BET method using low-temperature, low-humidity physical adsorption of an inert gas. Specifically, molecules with a known adsorption area, such as nitrogen, are 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 determined from the adsorption amount.

(c1) The shape of the inorganic filler is not particularly limited and can be of any shape. Therefore, from the viewpoint of expressing the effects such as formation of the above-described appropriate roughening surface and formation of a conductor layer with excellent adhesive strength, it is preferable to adjust the specific surface area to the above range, especially fumed silica and colloidal silica described later. Since the back is not spherical, regulation of the specific surface area is important.

As an inorganic filler with a specific surface area of 20 m2/g or more, a commercially available product may be used, such as fumed silica "AEROSIL (registered trademark) R972" (manufactured by Nippon Aerosil Co., Ltd., brand name, specific surface area 110 ± 20 m2) /g) and “AEROSIL (registered trademark) R202” (manufactured by Nippon Aerosil Co., Ltd., brand name, specific surface area 100±20 m2/g), colloidal silica “PL-1” (Fuso Chemical) Examples include “PL-7” (manufactured by Fuso Chemical Co., Ltd., brand name, specific surface area: 181 m2/g) and “PL-7” (manufactured by Fuso Chemical Co., Ltd., brand name, specific surface area: 36 m2/g).

(c1) As the inorganic filler, one that has been surface treated with a surface treatment agent such as a silane coupling agent may be used from the viewpoint of improving the moisture resistance of the resulting interlayer insulating layer.

As the inorganic filler surface-treated with a surface treatment agent, commercially available products may be used, such as "YC100C" (trade name, manufactured by Admatex Co., Ltd.), which is a silica filler treated with a phenylsilane coupling agent, and a silica filler treated with an epoxysilane coupling agent. “Sciqas Series” (manufactured by Sakai Chemical Industry Co., Ltd., brand name, 0.1 μm grade).

The content of the inorganic filler (c1) in the resin composition (1) is 3 to 50 parts by mass in terms of solid content of the resin composition (1) from the viewpoint of the laser processability of the resulting interlayer insulating layer and the adhesive strength of the conductor layer. Parts by mass are preferable, 5 to 40 parts by mass are more preferable, 6 to 30 parts by mass are still more preferable, 7 to 25 parts by mass are particularly preferable, and 8 to 20 parts by mass are most preferable. (c1) If the content of the inorganic filler is 3 parts by mass or more, good laser processing properties tend to be obtained, and if the content of the inorganic filler is 50 parts by mass or less, the adhesive strength of the conductor layer formed by the plating method tends to be excellent.

<(d1) polyamide resin>

The resin composition (1) also contains (d1) polyamide resin. In addition, in the present invention, “polyamide resin” means a polymer having an amide bond (-NHCO-) in the main chain, and the polyamideimide resin having an amide bond and an imide bond is defined as “polyamide resin” in the present invention. It shall not be included in “polyamide resin.”

(d1) Polyamide resin may be used individually or in combination of two or more types.

(d1) As the polyamide resin, a known polyamide resin can be used, which contains a polybutadiene skeleton from the viewpoint of obtaining an interlayer insulating layer with small surface roughness and excellent adhesive strength of the conductor layer formed by the plating method. It is preferable that it contains a phenolic hydroxyl group, an amino group, etc. that react with a thermosetting resin (for example, an epoxy group of an epoxy resin).

Examples of such (d1) polyamide resin include a structural unit represented by the following general formula (d-1), a structural unit represented by the following general formula (d-2), and a structural unit represented by the following general formula (d-3) A polyamide resin containing (hereinafter also referred to as “modified polyamide resin”) is preferable.

In general formulas (d-1) to (d-3), a, b, c, x, y and z are each the average degree of polymerization, a is an integer of 2 to 10, b is an integer of 0 to 3, c represents an integer of 3 to 30, y+z=2 to 300 ((y+z)/x) for x=1, and z≥20(z/y) for y=1.

R, R', and R'' are each independently a divalent group derived from aromatic diamine or aliphatic diamine, and R''' is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or a carboxyl group at both ends. It is a divalent group derived from an oligomer having

As aromatic diamines used in the production of the modified polyamide resin, diaminobenzene, diaminotoluene, diaminophenol, diaminodimethylbenzene, diaminomesitylene, diaminonitrobenzene, diaminodiazobenzene, diaminonaphthalene, Diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, diaminodimethyldiphenyl ether, methylenediamine, methylenebis(dimethylaniline), methylenebis(methoxyaniline), methylenebis(dimethoxyaniline) , methylenebis(ethylaniline), methylenebis(diethylaniline), methylenebis(ethoxyaniline), methylenebis(diethoxyaniline), isopropylidenedianiline, diaminobenzophenone, diaminodimethylbenzophenone, dia Minoanthraquinone, diaminodiphenylthioether, diaminodiphenyldiphenylthioether, diaminodiphenylsulfone, diaminodiphenylsulfoxide, diaminofluorene, etc. are mentioned.

Examples of aliphatic diamines used in the production of the modified polyamide resin include ethylenediamine, propanediamine, hydroxypropanediamine, butanediamine, heptanediamine, hexanediamine, diaminoethylamine, diaminopropylamine, cyclopentanediamine, and cyclohexane. Diamine, azapentanediamine, triazaundecadiamine, etc. can be mentioned.

Examples of dicarboxylic acids containing phenolic hydroxyl groups used in the production of the modified polyamide resin include hydroxyisophthalic acid, hydroxyphthalic acid, hydroxyterephthalic acid, dihydroxyisophthalic acid, and dihydroxyterephthalic acid.

Examples of dicarboxylic acids that do not contain phenolic hydroxyl groups used in the modified polyamide resin include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and oligomers having carboxyl groups at both ends.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, biphenyldicarboxylic acid, methylene 2 benzoic acid, thio 2 benzoic acid, carbonyl 2 benzoic acid, sulfonylbenzoic acid, naphthalenedicarboxylic acid, etc.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth)acryloyloxysuccinic acid, and di(meth)acrylic acid. Examples include monooxysuccinic acid, (meth)acryloyloxymalic acid, (meth)acrylamide succinic acid, and (meth)acrylamide malic acid.

Each raw material used in the production of the modified polyamide resin may be used individually, or two or more types may be used in combination.

(d1) As the polyamide resin, a commercially available product may be used. Examples of commercially available (d1) polyamide resins include polyamide resins “BPAM-01” and “BPAM-155” (all brand names) manufactured by Nippon Kayaku Co., Ltd.

Among these, "BPAM-155" is preferable from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method. “BPAM-155” is a rubber-modified polyamide having an amino group at the terminal, and has reactivity with an epoxy group. Therefore, the interlayer insulating layer obtained from a resin composition using “BPAM-155” as the (d1) polyamide resin can be formed using a plating method. The adhesive strength of the conductor layer formed by this method is superior, and the surface roughness tends to be reduced.

(d1) The number average molecular weight of the polyamide resin is preferably 20,000 to 30,000, more preferably 22,000 to 29,000, and 24,000 to 28,000 from the viewpoint of obtaining an interlayer insulating layer with excellent adhesive strength of the conductor layer formed by the plating method. This is more preferable.

(d1) The weight average molecular weight of the polyamide resin is preferably 100,000 to 140,000, more preferably 103,000 to 130,000, and 105,000 to 120,000 from the viewpoint of obtaining an interlayer insulating layer with excellent adhesive strength of the conductor layer formed by the plating method. This is more preferable. (d1) The number average molecular weight and weight average molecular weight of the polyamide resin can be measured by the method described in the Examples.

The content of polyamide resin (d1) in the resin composition (1) is 1 to 1 from the viewpoint of the surface roughness of the interlayer insulating layer and the adhesive strength of the conductor layer obtained with respect to 100 parts by mass in terms of solid content of the resin composition (1). 20 parts by mass is preferable, 2 to 15 parts by mass is more preferable, 3 to 12 parts by mass is more preferable, and 4 to 10 parts by mass is particularly preferable. (d1) If the polyamide resin content is 1 part by mass or more, the adhesive strength of the conductor layer formed by the plating method tends to be excellent, and if it is 20 parts by mass or less, when the interlayer insulating layer is roughened with an oxidizing agent, , the increase in surface roughness of the interlayer insulating layer tends to be suppressed.

<(e1) phenoxy resin>

The resin composition (1) preferably contains (e1) phenoxy resin.

(e1) By containing the phenoxy resin, the adhesive strength between the resulting interlayer insulating layer and the conductor layer tends to improve, and the surface roughening shape of the interlayer insulating layer tends to be small and dense. Additionally, when a conductor layer is formed on an interlayer insulating layer using an electroless plating method, the occurrence of plating blisters is suppressed and the adhesive strength between the interlayer insulating layer and the solder resist tends to improve.

(e1) Phenoxy resin may be used individually or in combination of two or more types.

(e1) The weight average molecular weight of the phenoxy resin is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, and 10,000 to 10,000 from the viewpoint of solubility in organic solvents and improving the mechanical strength and chemical resistance of the interlayer insulating layer. 50,000 is more preferable. (e1) By keeping the weight average molecular weight of the phenoxy resin within the above range, the occurrence of blisters in the conductor layer tends to be suppressed.

(e1) Phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol AF skeleton, bisphenol trimethylcyclohexane skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, and dicyclopenta. Examples include those having a diene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, trimethylcyclohexane skeleton, and copolymer skeleton of styrene and glycidyl methacrylate.

(e1) The phenoxy resin has a biphenyl skeleton from the viewpoint of improving the chemical resistance of the interlayer insulating layer and from the viewpoint of facilitating imparting appropriate irregularities to the interlayer insulating layer with an oxidizing agent in roughening, desmear treatment, etc. A phenoxy resin having an alicyclic structure is preferable, and from the viewpoint of both suppression of irregularities (hereinafter also referred to as “undulation”) on the surface of the interlayer insulating layer obtained and the storage stability of the resin composition, a phenoxy resin containing an alicyclic structure is preferred. desirable.

Here, “alicyclic structure” means “organic compounds with a structure in which carbon atoms are bonded in a ring, excluding aromatic compounds.” Among these, the alicyclic structure is preferably at least one selected from the group consisting of cyclic saturated hydrocarbons (cycloalkanes) and cyclic unsaturated hydrocarbons containing one double bond in the ring (cycloalkenes).

Examples of the phenoxy resin containing an alicyclic structure include a phenoxy resin containing a cyclohexane structure, a phenoxy resin containing a trimethylcyclohexane (hereinafter also referred to as “TMC”) structure, a phenoxy resin containing a terpene structure, etc. can be mentioned. Among these, from the viewpoint of excellent storage stability and reducing irregularities on the surface of the interlayer insulating layer, phenoxy resins containing at least one selected from the group consisting of a terpene structure and a TMC structure are preferred, and phenoxy resins containing a TMC structure are preferred. City resin is more preferable.

Examples of the phenoxy resin containing the TMC structure include the phenoxy resin disclosed in Japanese Patent Application Laid-Open No. 2006-176658.

As a phenoxy resin containing a terpene structure, for example, in the phenoxy resin disclosed in Japanese Patent Application Laid-Open No. 2006-176658, the dihydric phenol compound of the raw material is bis(4-hydroxyphenyl)- Examples include phenoxy resins synthesized using terpenediphenol instead of 3,3,5-trimethylcyclohexane.

The weight average molecular weight of the phenoxy resin containing at least one selected from the group consisting of the terpene structure and the trimethylcyclohexane structure is preferably 2,000 to 100,000, more preferably 10,000 to 60,000, and even more preferably 12,000 to 50,000. 15,000 to 45,000 is even more preferable, 17,000 to 40,000 is particularly preferable, and 20,000 to 37,000 is very preferable. If the weight average molecular weight of the phenoxy resin is more than the above lower limit, excellent peeling strength from the conductor layer tends to be obtained, and if it is less than the above upper limit, an increase in roughness and an increase in thermal expansion coefficient can be prevented.

(e1) As the phenoxy resin, a commercially available product may be used. Commercially available (e1) phenoxy resins include "YL7383" and "YL7384", which are phenoxy resins containing a bisphenol AF skeleton (all manufactured by Mitsubishi Chemical Corporation, brand names), and "1256", which are phenoxy resins containing a bisphenol A skeleton. “4250” (all manufactured by Mitsubishi Chemical Corporation, brand name), “YP-50” (manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., brand name), and “YX8100” (all manufactured by Mitsubishi Chemical Corporation, a phenoxy resin containing a bisphenol S skeleton) "YX6954", a phenoxy resin containing a bisphenol acetophenone skeleton (manufactured by Mitsubishi Chemical Corporation, brand name), "FX-293", a phenoxy resin containing a fluorene skeleton (Shinnittetsu Sumi) Kin Chemical Co., Ltd., brand name), “YL7213”, a phenoxy resin containing a bisphenol trimethylcyclohexane skeleton (Mitsubishi Chemical Co., Ltd., brand name), others, “FX-280” (Shinnittetsu Sumikin Chemical Co., Ltd.) (manufactured by Mitsubishi Chemical Corporation, brand name), “YL7553”, “YL6794”, “YL7290”, “YL7482” (above, manufactured by Mitsubishi Chemical Corporation, brand name), biphenyl type epoxy, and bisphenol TMC (1,1- and "YX7200B35" (manufactured by Mitsubishi Chemical Corporation, brand name) containing a bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane) skeleton.

(e1) There is no particular limitation on the method for producing the phenoxy resin, but for example, a known phenoxy resin may be prepared using a bisphenol compound containing a TMC structure or a bisphenol compound containing a terpene structure and a bifunctional epoxy resin as raw materials. It can be easily manufactured by reacting the epoxy group and the phenolic hydroxyl group in an equivalent ratio of about 1:0.9 to 1:1.1 according to the manufacturing method.

(e1) The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

The content of the phenoxy resin (e1) in the resin composition (1) is 3 to 30 parts by mass in terms of solid content of the resin composition (1) from the viewpoint of obtaining an interlayer insulating layer with high adhesion to the conductor layer. Parts by mass are preferable, 4 to 15 parts by mass are preferable, 5 to 13 parts by mass are more preferable, and 6 to 12 parts by mass are particularly preferable. (e1) If the content of the phenoxy resin is 1 part by mass or more, an increase in the amount of resin dissolved during desmearing is suppressed, and there is a tendency to prevent a decrease in peel strength, and if the content of the phenoxy resin is 30 parts by mass or less, the surface roughness There is a tendency to suppress a decrease in peel strength by suppressing it from becoming too small.

<(f1) Curing accelerator>

The resin composition (1) preferably contains a curing accelerator (f1) from the viewpoint of enabling curing at a low temperature in a short period of time.

(f1) A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

(f1) Examples of the curing accelerator include metal-based curing accelerators such as organic metal salts; Organic curing accelerators such as imidazole compounds, phosphorus-based curing accelerators, and amine-based curing accelerators can be mentioned.

(Metallic hardening accelerator)

Examples of the metal-based curing accelerator include organic metal-based curing accelerators. The organometallic curing accelerator has an effect of promoting the self-polymerization reaction of (a1) cyanate resin and an effect of promoting the reaction of (a1) cyanate resin and (b1) epoxy resin.

Examples of organometallic curing accelerators include transition metals, organometallic salts of Group 12 metals, and organometallic complexes. Examples of metals include copper, cobalt, manganese, iron, nickel, zinc, and tin.

Examples of organometallic salts include carboxylates, and specific examples thereof include naphthenates such as cobalt naphthenate and zinc naphthenate; 2-ethylhexanoate such as cobalt 2-ethylhexanoate and zinc 2-ethylhexanoate; Octylate salts such as zinc octylate, tin octylate, and cobalt octylate; and stearates such as tin stearate and zinc stearate.

Examples of the organic metal complex include chelate complexes such as acetylacetone complex, and specific examples thereof include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate; Organic copper complexes such as copper(II) acetylacetonate; Organic zinc complexes such as zinc (II) acetylacetonate; Organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate; and organic manganese complexes such as manganese (II) acetylacetonate. Among these, from the viewpoint of curability and solubility in solvents, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, iron (III) acetylacetonate, zinc naphthenate, and naphthate. Cobalt tenate is preferred.

When the resin composition (1) contains a metallic curing accelerator, the content of the metallic curing accelerator is determined by the solid content mass of (a1) cyanate resin from the viewpoint of obtaining sufficient reactivity and curability and suppressing the curing rate from becoming too high. In terms of mass, 1 to 200 ppm is preferable, 1 to 75 ppm is more preferable, and 1 to 50 ppm is still more preferable. The metal-based hardening accelerator may be blended all at once, or may be blended in multiple portions.

(Organic hardening accelerator)

Preferred organic curing accelerators include imidazole compounds, phosphorus-based curing accelerators, and amine-based curing accelerators from the viewpoint of smear removal in via holes.

[Imidazole compound]

Imidazole compounds and their derivatives include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 1,2-dimethyl. Imidazole, 2-ethyl-1-methylimidazole, 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl -2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2 -Ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Sol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 2,4-diamino-6- [2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]ethyl-s-triazine imidazole compounds such as azine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine; Trimellitic acid adduct of the above imidazole compound; Isocyanuric acid adduct of the above imidazole compound; Hydrobromic acid adducts of the above imidazole compounds, etc. can be mentioned. Among these, 1-cyanoethyl-2-phenylimidazole is preferable from the viewpoints of solubility in varnish, storage stability of the resulting film, thermal expansion coefficient of the cured product, and surface roughening shape by desmear.

[Amine-based hardening accelerator]

Examples of the amine-based curing accelerator include amine-based compounds such as secondary amines and tertiary amines; Quaternary ammonium salts, etc. can be mentioned.

As an amine-based curing accelerator, a commercially available product may be used. Examples of commercially available amine-based curing accelerators include amine adduct compounds such as “Novacure (registered trademark)” (Asahi Kasei Co., Ltd., brand name) and “Fuji Cure (registered trademark)” (Fuji Kasei Co., Ltd., brand name); and amine compounds such as 1,8-diazabicyclo[5.4.0]undecene 7, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tris(dimethylaminomethyl)phenol.

[Phosphorus-based hardening accelerator]

As a phosphorus-based curing accelerator, an organophosphorus-based compound is preferable. Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and tris(p-methylphenyl). ) Phosphine, tricyclohexylphosphine, triphenylphosphine/triphenylborane complex, tetraphenylphosphonium tetraphenylborate, etc. are mentioned. Additionally, the phosphorus-based curing accelerator may be an addition reaction product of these phosphine compounds and a quinone compound, as shown in Japanese Patent Application Laid-Open No. 2011-179008, or tris(p-methylphenyl)phosphine and 1,4-benzo. It is preferable that it is an addition reaction product of quinone.

When the resin composition (1) contains an organic curing accelerator, the content of the organic curing accelerator is 100 mass equivalents of the solid content of the epoxy resin (b1) from the viewpoint of obtaining sufficient reactivity and curability and suppressing the curing rate from becoming too high. The amount 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.

<(g1) Epoxy resin hardener>

The resin composition (1) may further contain an epoxy resin curing agent (g1).

(g1) The epoxy resin curing agent may be used individually or in combination of two or more types.

(g1) Examples of the epoxy resin curing agent include various phenolic compounds such as bifunctional phenol resins; acid anhydrides such as phthalic anhydride, benzophenone tetracarboxylic dianhydride, and methyl hymic acid; Hydrazides, amines, active ester curing agents described later, and dicyandiamide can be mentioned.

<Other ingredients>

The resin composition (1) may contain components other than the above components as long as they do not impair the effects of the present invention.

Examples of other components include resin components other than the above components (hereinafter also referred to as “other resin components”), additives, flame retardants, organic solvents, etc.

Other resin components include thermosetting resins and thermoplastic resins other than the components mentioned above.

As for the thermosetting resin, which is another resin component, it is preferable to thermoset at 150 to 200°C. This temperature corresponds to the heat curing temperature usually used when forming the interlayer insulating layer of a multilayer printed wiring board. Examples of such thermosetting resins include polymers of bismaleimide compounds and diamine compounds, bismaleimide compounds, bisallylnadide resins, and benzoxazine compounds.

As additives, thickeners such as orbene and bentone; Adhesion imparting agents such as imidazole-based, thiazole-based, triazole-based, and silane coupling agents; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black; Organic fillers such as rubber particles, etc. can be mentioned.

Examples of flame retardants include inorganic flame retardants and resin flame retardants. Examples of the inorganic flame retardant include aluminum hydroxide and magnesium hydroxide, which are exemplified as (c1) inorganic fillers. The resin flame retardant may be a halogen-based resin or a non-halogen-based resin, but out of consideration for environmental impact, a non-halogen-based resin is preferable. The resin flame retardant may be blended as a filler or may have a functional group that reacts with the thermosetting resin.

(organic solvent)

The resin composition (1) may be in a varnish state by containing an organic solvent from the viewpoint of facilitating handling and facilitating formation of the resin film for the interlayer insulating layer described later.

Organic solvents may be used individually or in combination of two or more types.

Examples of organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), methyl isobutyl ketone, and cyclohexanone; Acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; Carbitol-based solvents such as Cellosolve and butylcarbitol; Aromatic hydrocarbon-based solvents such as toluene and xylene; and amide-based solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these, from the viewpoint of solubility, ketone solvents are preferable, and MEK and methyl isobutyl ketone are more preferable.

When the resin composition (1) is in the form of a varnish, the content of the organic solvent may be appropriately adjusted to a range that makes the resin composition (1) easy to handle and a range that improves the coatability of the varnish. The solid content concentration (concentration of components other than the organic solvent) in the varnish is preferably 10 to 50 mass%, more preferably 15 to 50 mass%, and still more preferably 20 to 40 mass%.

<Method for producing resin composition (1)>

Resin composition (1) can be manufactured by mixing each of the above components. As a mixing method, a known method can be applied, for example, mixing can be done using a bead mill or the like.

[Resin composition (2)]

The resin composition (2) of the present invention consists of (a2) cyanate resin, (b2) epoxy resin, and (c2) inorganic filler, (e2) phenoxy resin, (f2) curing accelerator, and (g2) epoxy resin curing agent. It is a resin composition containing one or more types selected from the group.

<(a2) cyanate resin>

(a2) Cyanate resin has the same description as that of (a1) cyanate resin, and its preferred embodiments are also the same.

The content of cyanate resin (a2) in the resin composition (2) is determined from the viewpoint of adhesion to the conductor layer, storage stability, heat resistance, low heat expansion, smear removal properties, dielectric properties, and undulation suppression. The amount is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and especially preferably 3 to 12 parts by mass, based on 100 parts by mass in terms of solid content.

<(b2) epoxy resin>

The (b2) epoxy resin is not particularly limited, but includes the same epoxy resin as the (b1) epoxy resin.

(b2) Epoxy resins may be used individually, or two or more types may be used together.

Among these epoxy resins, from the viewpoint of storage stability, heat resistance, and smear removability, novolak-type epoxy resins are preferable, and at least one type of structural unit represented by any of the following general formulas (b-3) to (b-5) A novolak-type epoxy resin having is more preferable.

In general formulas (b-3) to (b-5), R ^b2 represents a hydrogen atom or a methyl group.

The structural unit represented by general formula (b-3) is preferably a structural unit represented by the following formula (b-3') or (b-3'').

The novolak-type epoxy resin contains at least one type of structural unit represented by any of the above general formulas (b-3) to (b-5), thereby providing excellent dielectric properties, a low coefficient of thermal expansion, and a conductor layer. An interlayer insulating layer with excellent adhesiveness tends to be obtained.

The content of the structural unit represented by any of the general formulas (b-3) to (b-5) in the novolak-type epoxy resin is preferably 70 mol% or more, and 80 mol% or more in terms of molar concentration. More preferably, 90 mol% or more is still more preferable, may be substantially 100 mol%, and in terms of mass concentration, 70 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is still more preferable. , may be substantially 100% by mass.

(b2) The epoxy resin is a novolac represented by any of the following general formulas (b-6) to (b-8) from the viewpoint of obtaining an interlayer insulating layer with excellent dielectric properties, coefficient of thermal expansion, and adhesion to the conductor layer. It is preferable that it is a type epoxy resin.

In any of the above general formulas (b-6) to (b-8), R ^b2 is as described above, and n represents an integer of 1 to 20, preferably an integer of 1 to 10.

In addition, the (b2) epoxy resin is preferably an epoxy resin containing a naphthalene skeleton, more preferably a novolak-type epoxy resin containing a naphthalene skeleton, from the viewpoint of heat resistance, low thermal expansion, rigidity, and high frequency characteristics, and the following general A naphthol novolak-type epoxy resin containing a structural unit represented by formula (b-9) is more preferable.

In general formula (b-9), R ^b3 represents an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom.

In an epoxy resin containing the structural unit represented by the general formula (b-9), the content of the structural unit represented by the general formula (b-9) is 50% from the viewpoint of heat resistance, low thermal expansion, rigidity, and high frequency characteristics. - 100 mass % is preferable, 70-100 mass % is more preferable, and 80-100 mass % is still more preferable.

A commercially available novolak-type epoxy resin can be used. Commercially available novolak-type epoxy resins include “N673” (epoxy equivalent: 211 g/eq), “N698” (epoxy equivalent: 218 g/eq), “N740” (epoxy equivalent: 180 g/eq), and “N770” (epoxy equivalent). Equivalent weight: 188 g/eq), “N775” (epoxy equivalent weight: 187 g/eq), “N730-A” (epoxy equivalent weight: 175 g/eq) (above, manufactured by DIC Corporation, brand name), “NC-2000-L” ” (Epoxy equivalent weight: 237 g/eq), “NC-3000-H” (Epoxy equivalent weight: 289 g/eq), “NC-7000-L” (Epoxy equivalent weight: 231 g/eq) (manufactured by Nihon Kayaku Co., Ltd., Product name) (above, manufactured by Nippon Kayaku Co., Ltd., product name), etc.

(b2) The epoxy equivalent weight of the epoxy resin is preferably 150 to 500 g/eq, and is 150 to 400 g from the viewpoints of adhesion to the conductor layer, storage stability, heat resistance, smear removability, undulation suppression, and surface roughness after desmear. /eq is more preferable, and 150 to 300 g/eq is still more preferable.

The content of the (b2) epoxy resin in the resin composition (2) is determined by the resin composition ( 2), based on 100 parts by mass in terms of solid content, is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, more preferably 7 to 40 parts by mass, and especially preferably 8 to 35 parts by mass.

In the resin composition (2), the mass ratio [(a2)/(b2)] of (a2) cyanate resin and (b2) epoxy resin is determined by adhesion to the conductor layer, storage stability, low thermal expansion, dielectric properties, and heat resistance. , from the viewpoint of undulation suppression, smear removal properties and surface roughness after desmearing, 0.1 to 3 is preferable, 0.2 to 2.5 is more preferable, 0.2 to 1.25 is more preferable, and 0.25 to 1.25 is especially preferable. If the mass ratio is 0.1 or more, the amount of (a2) cyanate resin does not become too small, and good high-frequency characteristics tend to be obtained. If it is 3 or less, the amount of (a2) cyanate resin does not become too large, and hardening occurs. There is a tendency to suppress the rise in temperature.

<(c2) Inorganic filler>

The resin composition (2) also contains (c2) an inorganic filler.

By containing the inorganic filler (c2), the resin composition (2) tends to achieve good embedding properties in circuit boards, especially when laminating a resin film for an interlayer insulating layer produced using the resin composition (2) described later. It tends to have excellent fluidity (integration of circuit patterns).

(c2) Inorganic fillers may be used individually or in combination of two or more types.

The (c2) inorganic filler is not particularly limited, but includes the same things as the (c1) inorganic filler. Among these, silica is preferable from the viewpoint of thermal expansion coefficient, varnish handleability, and insulation reliability.

(c2) The shape of the inorganic filler is preferably spherical from the viewpoint of making it easy to fill the through holes formed in the inner layer circuit and the irregularities of the circuit pattern, and from the same viewpoint, it is preferably spherical silica.

(c2) The volume average particle size of the inorganic filler is 0.05 to 0.05 from the viewpoint of good embedding properties of the circuit board and insulation reliability between layers and interconnections, and from the viewpoint of stably forming a fine pattern when forming a circuit pattern in the interlayer insulating layer. 10 μm is preferable, 0.1 to 5 μm is more preferable, 0.2 to 3 μm is still more preferable, and 0.3 to 2 μm is particularly preferable.

In this specification, the volume average particle size is the particle size at the point corresponding to 50% of the volume when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%, and is a particle size distribution measuring device using a laser diffraction scattering method. It can be measured, etc.

(c2) As silica used as an inorganic filler, commercially available products may be used, and examples include the "Admapain (registered trademark)" (trade name) series, which is a high-purity synthetic spherical silica (manufactured by Admatex Co., Ltd., brand name). Among the “Admapain (registered trademark)” series, “SO-C1” (volume average particle size: 0.25㎛), “SO-C2” (volume average particle size: 0.5㎛), and “SO-” are highly purified and contain few ionic impurities. C3” (volume average particle size: 0.9 μm), “SO-C5” (volume average particle size: 1.6 μm), “SO-C6” (volume average particle size: 2.2 μm), etc. Additionally, these may be subjected to surface treatment with a silane coupling agent described later, mixed with a solvent, and then passed through a filter to cut off coarse particles.

(c2) As the inorganic filler, it is preferable to use silica surface-treated with a surface treatment agent such as a silane coupling agent from the viewpoint of improving moisture resistance.

Silane coupling agents include aminosilane coupling agents (hereinafter simply referred to as “aminosilane”), vinylsilane coupling agents (hereinafter simply referred to as “vinylsilane”), and epoxysilane coupling agents (hereinafter simply referred to as “epoxysilane”). ), etc. (c2) The inorganic filler is preferably surface treated with at least one surface treatment agent selected from the group consisting of vinyl silane, epoxy silane, and amino silane, and from the viewpoint of smear removal properties, it is more preferable to be surface treated with amino silane. .

Silica that has been subjected to these surface treatments may be used individually, or silica that has been treated with another silane coupling agent may be used in combination.

In addition, when silica surface-treated with epoxysilane is used, the surface roughness after the roughening treatment process described later is small and the resin composition tends to have excellent storage stability, and when silica surface-treated with vinylsilane is used, storage stability and Smear removal properties tend to be excellent.

When a resin composition containing a conventional cyanate resin was used as a material for the interlayer insulating layer, heat resistance and storage stability were not necessarily satisfactory. In addition, the material forming the interlayer insulating layer should be able to easily remove smear (resin residue) generated when forming via holes with a laser, etc. in a later desmear treatment (must have excellent smear removal properties). This is being desired.

The resin composition (2) contains silica surface-treated with at least one silane coupling agent selected from the group consisting of epoxy silane and vinyl silane, thereby improving storage stability, reflow heat resistance and smear removability of the resulting interlayer insulating layer. They tend to be highly compatible.

Additionally, by mixing the two at an optimal ratio, the storage stability of the resin composition and the resulting interlayer insulating layer tend to have excellent smear removal properties and reflow heat resistance.

In addition, from the viewpoint of achieving both the above-mentioned effects, the silica preferably contains silica surface-treated with epoxysilane and silica surface-treated with vinylsilane.

When the silica contains silica surface-treated with epoxysilane and silica surface-treated with vinylsilane, the content ratio of silica surface-treated with epoxysilane is silica surface-treated with epoxysilane and silica surface-treated with vinylsilane. With respect to the total content of silica, 10 to 90 mass% is preferable, 20 to 80 mass% is more preferable, and 25 to 60 mass% is still more preferable.

The epoxysilane used for surface treatment of silica is not particularly limited as long as it is a silane coupling agent containing an epoxy group, but from the viewpoint of obtaining an interlayer insulating layer with low surface roughness after the roughening treatment process and excellent storage stability. , a silane coupling agent having one or two epoxy groups and one silicon atom is preferable, and a silane coupling agent having one epoxy group and one silicon atom is more preferable.

Examples of such epoxysilanes include epoxysilanes represented by the following general formula (c-1).

In general formula (c-1), R ^c1 and R ^c2 each independently represent an alkyl group having 1 to 12 carbon atoms, R ^c3 represents an alkylene group having 1 to 12 carbon atoms, and It represents a monovalent group represented by c-2) or (c-3). s represents an integer from 1 to 3. When s is 1, a plurality of R ^c2 groups may be the same or different, and when s is 2 or 3, a plurality of R ^c1 groups may be the same or different.

The number of carbon atoms of the alkyl group represented by R ^c1 or R ^c2 is preferably 1 to 6, and more preferably 1 to 3. Specifically, methyl group, ethyl group, propyl group, etc. are mentioned, and among these, methyl group or ethyl group is preferable.

The number of carbon atoms of the alkylene group represented by R ^c3 is preferably 1 to 6, and more preferably 2 to 4. Specifically, methylene group, ethylene group, 1,3-propylene group, etc. are mentioned, and among these, 1,3-propylene group is preferable.

As the epoxysilane, a commercially available product may be used. Commercially available epoxysilanes include “KBM-303” (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane), “KBM-402” (3-glycidoxypropylmethyldimethoxysilane), and “KBM.” -403” (3-glycidoxypropyltrimethoxysilane), “KBE-402” (3-glycidoxypropylmethyldiethoxysilane), “KBE-403” (3-glycidoxypropyltriethoxysilane) ) (above, manufactured by Shinetsu Kagaku Kogyo Co., Ltd., brand name), etc. Among these, "KBM-403" is preferable from the viewpoint of obtaining an interlayer insulating layer excellent in reflow heat resistance, storage stability, and smear removal properties.

The vinyl silane is not particularly limited as long as it is a silane coupling agent containing a vinyl group, but from the viewpoint of obtaining an interlayer insulating layer with excellent storage stability and excellent smear removal properties, for example, one or two vinyl groups and one silicon A silane coupling agent having an atom is preferable, and a silane coupling agent having one vinyl group and one silicon atom is more preferable.

Examples of such vinyl silane coupling agents include vinyl silane coupling agents represented by the following general formula (c-4).

In general formula (c-4), R ^c4 and R ^c5 each independently represent an alkyl group having 1 to 12 carbon atoms, R ^c6 represents a single bond or an alkylene group having 1 to 12 carbon atoms, and t is 1. It represents an integer from to 3. When t is 1, a plurality of R ^c5 groups may be the same or different, and when t is 2 or 3, a plurality of R ^c4 groups may be the same or different.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^c4 or R ^c5 include those that are the same as R ^c1 and R ^c2 in the general formula (c-1) above, and the preferred embodiments are also the same.

Examples of the alkylene group having 1 to 12 carbon atoms represented by R ^c6 include the same alkylene groups as R ^c3 in the general formula (c-1) above, and the preferred embodiments are also the same.

Among the groups represented by R ^c6 above, it is preferable that R ^c6 is a single bond.

As vinyl silane, a commercially available product may be used. Commercially available vinyl silanes include “KBM-1003” (vinyltrimethoxysilane), “KBE-1003” (vinyltriethoxysilane) (above, manufactured by Shinetsu Chemical Co., Ltd., brand name), etc. . Among these, "KBM-1003" with a short molecular chain is preferable from the viewpoint of embedding of the inner layer wiring.

As aminosilanes, "KBM-603" (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) (above , manufactured by Shin-Etsu Chemical Co., Ltd., brand name), etc., and from the viewpoint of reflow heat resistance, "KBM-573" is preferable.

These silicas may be used in the form of a silica slurry previously dispersed in a solvent.

The content of the inorganic filler (c2) in the resin composition (2) is preferably 40 to 90 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition (2) from the viewpoint of low thermal expansion, high frequency characteristics, and embedding in the wiring pattern. 50 to 85 parts by mass is more preferable, and 55 to 80 parts by mass is still more preferable. (c2) If the content of the inorganic filler is 40 parts by mass or more, good low thermal expansion properties and high frequency characteristics tend to be obtained, and if the content of the inorganic filler is 90 parts by mass or less, good embedding properties in the wiring pattern tend to be obtained.

From the same viewpoint, the content of the (c2) inorganic filler in the resin composition (2) is preferably 50 to 500 parts by mass with respect to 100 parts by mass in terms of solid content of the resin composition (2) excluding the (c2) inorganic filler, 150 to 300 parts by mass is more preferable, and 200 to 250 parts by mass is still more preferable.

<(e2) phenoxy resin>

It is preferable that the resin composition (2) further contains (e2) phenoxy resin.

By containing the phenoxy resin (e2), the resin composition (2) tends to improve the adhesive strength between the obtained interlayer insulating layer and the conductor layer, and also tends to make the surface roughening shape of the interlayer insulating layer small and dense. there is. Additionally, when a conductor layer is formed on an interlayer insulating layer using an electroless plating method, the occurrence of plating blisters is suppressed and the adhesive strength between the interlayer insulating layer and the solder resist tends to improve.

(e2) Phenoxy resin has the same explanation as that of (e1) phenoxy resin.

Among these phenoxy resins, the resin composition (2) is excellent in storage stability, has small surface irregularities of the resulting interlayer insulating layer, has good smear removal properties, and is suitable from the viewpoint of producing a resin composition with a small surface roughness after desmearing. It is preferred to contain a phenoxy resin containing a formula structure.

When using a conventional cyanate compound and an epoxy resin together, it has been found that when a polymer such as a phenoxy resin is added, it tends to be difficult to achieve both the suppression of undulation of the resulting interlayer insulating layer and the storage stability of the resin composition. , improvement was desired.

The resin composition (2) is a phenoxy resin (e2), and by containing a phenoxy resin containing an alicyclic structure, it is possible to achieve both, in particular, a high degree of both storage stability and suppression of surface undulation of the resulting interlayer insulating layer. The preferred embodiment of the phenoxy resin containing an alicyclic structure is explained in the same way as the explanation of the (e1) phenoxy resin.

When the resin composition (2) contains the phenoxy resin (e2), the content is preferably 0.05 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2). , 0.5 to 7 parts by mass is more preferable. (e2) If the content of the phenoxy resin is 0.05 parts by mass or more, sufficient flexibility is obtained and handleability is excellent, and the peeling strength of the conductor layer formed by plating tends to be excellent. If the content of the phenoxy resin is 20 parts by mass or less, Sufficient fluidity is obtained during lamination, and appropriate roughness tends to be obtained.

In addition, when the (e2) phenoxy resin is a phenoxy resin having the biphenyl skeleton, its content is preferably 0.05 to 10 parts by mass, and 0.2 to 5 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2). Parts by mass are more preferable, and 0.5 to 1.5 parts by mass are further preferable.

In addition, when the (e2) phenoxy resin is a phenoxy resin containing the above-mentioned alicyclic structure, the content is preferably 1 to 10 parts by mass, and 1.5 to 10 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2). 7 parts by mass is more preferable, and 2 to 6 parts by mass is still more preferable.

<(f2) Curing accelerator>

It is preferable that the resin composition (2) further contains a curing accelerator (f2).

The (f2) curing accelerator is not particularly limited, but includes the same curing accelerator as the (f1) curing accelerator.

(f2) A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

Among these, the curing accelerator (f2) is preferably at least one selected from the group consisting of the organometallic salt, the imidazole compound, the phosphorus-based curing accelerator, and the amine-based curing accelerator, and is suitable for its solubility in the varnish and the properties of the resulting film. From the viewpoint of storage stability, thermal expansion coefficient of the cured product, and surface roughening shape by desmear, imidazole compounds are more preferable, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-unde Silimidazolium trimellitate is more preferred, and 1-cyanoethyl-2-phenylimidazole is particularly preferred.

In addition, the resin composition (2) preferably contains a phosphorus-based curing accelerator as the curing accelerator (f2). By containing a phosphorus-based curing accelerator, curing becomes possible at a low temperature and in a short time, and the appearance and smear removal properties of the interlayer insulating layer obtained by curing while attached to a support are improved.

Here, when an organic insulating resin layer containing a conventional cyanate resin, epoxy resin, and active ester resin is laminated on a core substrate and cured while attached to a support, peeling occurs at the interface between the core substrate and the organic insulating resin layer after curing. This occurred, and there were cases where a cured substrate with a good appearance could not be obtained.

The resin composition (2) of the present invention contains a phosphorus-based curing accelerator, so that an interlayer insulating layer with a good appearance can be obtained even when cured in a state attached to a support. Moreover, the obtained interlayer insulating layer has a low dielectric loss tangent, making it easy to remove smear after laser processing. Tends to have excellent durability and heat resistance.

As a phosphorus-based curing accelerator, an organophosphorus-based compound is preferable.

Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, and tricyclohexylphosphine. , triphenylphosphine/triphenylborane complex, tetraphenylphosphonium tetraphenylborate, and addition reaction products of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound. Among these, the addition reaction product of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom is preferable, and is represented by the following general formula (f-1) as shown in Japanese Patent Application Laid-Open No. 2011-179008. It is preferable that it is an addition reaction product of a phosphine compound and a quinone compound represented by the following general formula (f-2).

In general formula (f-1), R ^f1 represents an alkyl group having 1 to 12 carbon atoms, and R ^f2 and R ^f3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In general formula (f-2), R ^f4 to R ^f6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^f4 and R ^f5 may be bonded to each other to form a cyclic structure.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^f1 in the general formula (f-1) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and pentyl group. , chain alkyl groups such as hexyl group, octyl group, decyl group, and dodecyl group; Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, and cyclohexenyl group; Aryl group-substituted alkyl groups such as benzyl group; Alkoxy group-substituted alkyl groups such as methoxy group-substituted alkyl groups, ethoxy-group-substituted alkyl groups, and butoxy-group-substituted alkyl groups; Amino group-substituted alkyl groups such as dimethylamino group and diethylamino group; A hydroxyl group substituted alkyl group etc. are mentioned.

Additionally, the hydrocarbon group having 1 to 12 carbon atoms represented by R ^f2 and R ^f3 includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups may be substituted with a substituent.

Examples of the aliphatic hydrocarbon group include the same alkyl group having 1 to 12 carbon atoms represented by R ^f1 above.

Examples of alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, and those substituted by alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. You can.

Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups and naphthyl groups; aryl groups substituted with alkyl groups such as tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl group, and dimethylnaphthyl group; Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, and methoxy naphthyl group; Amino group-substituted aryl groups such as dimethylamino group and diethylamino group; Halogen-substituted aryl groups such as hydroxyphenyl group and dihydroxyphenyl group; Aryloxy groups such as phenoxy group and crezoxy group; Examples include phenylthio group, tolylthio group, diphenylamino group, and those substituted with amino group, halogen, etc. Among them, substituted or unsubstituted alkyl groups and aryl groups are preferable.

Examples of the phosphine compound represented by the general formula (f-1) include trialkylphosphine such as tricyclohexylphosphine, tributylphosphine, and trioctylphosphine; Alkyldiphenylphosphine such as cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine, butyldiphenylphosphine, dibutylphenylphosphine, octyldiphenylphosphine, and dioctylphenylphosphine; Examples include dialkylphenylphosphine, but from the viewpoint of varnish solubility, tributylphosphine, tri(p-methylphenyl)phosphine, tri(m-methylphenyl)phosphine, and tri(o-methylphenyl)phosphine are preferred. do.

Examples of the hydrocarbon group having 1 to 18 carbon atoms represented by R ^f4 to R ^f6 in the general formula (f-2) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups may be substituted with a substituent.

Examples of aliphatic hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and dodecyl; Alkoxy groups such as allyl group, methoxy group, ethoxy group, propoxyl group, n-butoxy group, and tert-butoxy group; Alkylamino groups such as dimethylamino group and diethylamino group; Alkylthio groups such as methylthio group, ethylthio group, butylthio group, and dodecylthio group; Substituted alkyl groups such as amino group-substituted alkyl groups, alkoxy-substituted alkyl groups, hydroxyl-substituted alkyl groups, and aryl-substituted alkyl groups; and substituted alkoxy groups such as amino group-substituted alkoxy groups, hydroxyl-substituted alkoxy groups, and aryl-group-substituted alkoxy groups.

Examples of alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group, and those substituted with alkyl group, alkoxy group, aryl group, hydroxyl group, amino group, halogen, etc. You can.

Examples of aromatic hydrocarbon groups include aryl groups such as phenyl groups and tolyl groups; aryl groups substituted with alkyl groups such as dimethylphenyl group, ethylphenyl group, butylphenyl group, and t-butylphenyl group; Alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, and t-butoxyphenyl group; Aryloxy groups such as phenoxy group and crezoxy group; Examples include phenylthio group, tolylthio group, diphenylamino group, and those substituted with amino group, halogen, etc.

Among these, hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted alkylthio group and substituted or unsubstituted alkyl group. Ringed arylthio groups are preferred.

Additionally, the quinone compound represented by the general formula (f-2) may have a cyclic structure in which R ^f4 and R ^f5 are bonded. The polycyclic quinone compound in which R ^f4 and R ^f5 are bonded to form a cyclic structure is represented by any of the following general formulas (f-3) to (f-5) in which a substituted tetramethylene group, tetramethine group, etc. are bonded. polycyclic quinone compounds, etc.

In general formulas (f-3) to (f-5), R ^f6 is as described above.

Among the quinone compounds represented by the general formula (f-2), 1,4-benzoquinone and methyl-1,4-benzoquinone are preferred from the viewpoint of reactivity with phosphine compounds, and from the viewpoint of curability upon moisture absorption. In, alkoxy group-substituted 1,4-benzoquinone such as 2,3-dimethoxy-1,4-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, and methoxy-1,4-benzoquinone; Alkyl-substituted 1,4-benzoquinone, such as 2,3-dimethyl-1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, and methyl-1,4-benzoquinone, is preferred, and has good storage stability. From this point of view, 2,5-di-t-butyl-1,4-benzoquinone, t-butyl-1,4-benzoquinone, and phenyl-1,4-benzoquinone are preferred.

Examples of addition reactants of the phosphine compound represented by the general formula (f-1) and the quinone compound represented by the general formula (f-2) include compounds represented by the following general formula (f-6), etc. .

In general formula (f-6), R ^f1 to R ^f6 are the same as general formulas (f-1) and (f-2).

Among the addition reactants of a phosphine compound and a quinone compound in which at least one alkyl group is bonded to a phosphorus atom, from the viewpoint of curability upon moisture absorption, the addition reactants of tricyclohexylphosphine and 1,4-benzoquinone, tricyclohexylphosphine and Addition reaction product of methyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethyl-1,4-benzoquinone, tricyclohexylphosphine and 2,5-dimethyl-1,4- Addition reaction product of benzoquinone, addition reaction product of tricyclohexylphosphine and methoxy-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tricyclo Addition reaction product of hexylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of tributylphosphine and 1,4-benzoquinone, addition reaction product of tributylphosphine and methyl-1,4-benzoquinone Addition reactant, addition reactant of tributylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reactant of tributylphosphine and 2,5-dimethyl-1,4-benzoquinone, tributylphosphine and Addition reaction product of methoxy-1,4-benzoquinone, addition reaction product of tributylphosphine and 2,3-dimethoxy-1,4-benzoquinone, tributylphosphine and 2,5-dimethoxy-1,4 -Addition reaction product of benzoquinone, addition reaction product of trioctylphosphine and 1,4-benzoquinone, addition reaction product of trioctylphosphine and methyl-1,4-benzoquinone, trioctylphosphine and 2,3-dimethyl- Addition reaction product of 1,4-benzoquinone, addition reaction product of trioctylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and methoxy-1,4-benzoquinone, tri Trialkylphosphine and quinone, such as the addition reaction product of octylphosphine and 2,3-dimethoxy-1,4-benzoquinone, and the addition reaction product of trioctylphosphine and 2,5-dimethoxy-1,4-benzoquinone. Addition reactants of the compounds are preferred.

In addition, from the viewpoint of reflow crack resistance, the addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, the addition reaction product of cyclohexyldiphenylphosphine and methyl-1,4-benzoquinone, and cyclohexyldiphenylphosphine. Addition reaction product of pin and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and methoxy -Addition reaction product of 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, cyclohexyldiphenylphosphine and 2,5-dimethoxy-1 , addition reaction product of 4-benzoquinone, addition reaction product of butyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and methyl-1,4-benzoquinone, butyldiphenylphosphine and 2 ,Addition reaction product of 3-dimethyl-1,4-benzoquinone, addition reaction product of butyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, butyldiphenylphosphine and methoxy-1,4- Addition reaction product of benzoquinone, addition reaction product of butyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition of butyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone Reactant, addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methyl-1,4-benzoquinone, octyldiphenylphosphine and 2,3-dimethyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and methoxy-1,4-benzoquinone, jade Addition reaction product of tyldiphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, dicyclohexylphenylphos Addition reaction product of pin and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methyl-1,4-benzoquinone, dicyclohexylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone Discussion Addition reaction product, addition reaction product of dicyclohexylphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and methoxy-1,4-benzoquinone, dicyclohexyl Addition reaction product of phenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, dibutylphenylphosphine Addition reaction product of methyl-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, dibutylphenylphosphine and 2,5-dimethyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of dibutylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dibutylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, di Addition reaction product of butylphenylphosphine and 2,5-dimethoxy-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 1,4-benzoquinone, dioctylphenylphosphine and methyl-1,4- Addition reaction product of benzoquinone, addition reaction product of dioctylphenylphosphine and 2,3-dimethyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 2,5-dimethyl-1,4-benzoquinone, Addition reaction product of dioctylphenylphosphine and methoxy-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and 2,3-dimethoxy-1,4-benzoquinone, dioctylphenylphosphine and 2, Addition reactants of alkyldiphenylphosphine or dialkylphenylphosphine and quinone compounds, such as addition reactants of 5-dimethoxy-1,4-benzoquinone, are preferable, and among them, cyclohexyldiphenylphosphine and 1,4 -Alkyldiphenylphosphine and 1,4-, such as the addition reaction product of benzoquinone, the addition reaction product of butyldiphenylphosphine and 1,4-benzoquinone, and the addition reaction product of octyldiphenylphosphine and 1,4-benzoquinone. The addition reactant of benzoquinone is more preferred.

Additionally, from the viewpoint of storage stability, the addition reaction product of tricyclohexylphosphine and t-butyl-1,4-benzoquinone, the addition reaction product of tributylphosphine and t-butyl-1,4-benzoquinone, and trioctylphosphine. Addition reaction product of pin and t-butyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and t-butyl-1,4-benzoquinone, dibutylphenylphosphine and t-butyl-1,4 -Addition reaction product of benzoquinone, addition reaction product of dioctylphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone, butyldi Addition reaction product of phenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of octyldiphenylphosphine and t-butyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and t- Addition reaction product of butyl-1,4-benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and t-butyl-1,4-benzoquinone, dioctyl-p-tolylphosphine and t-butyl-1, Addition reaction product of 4-benzoquinone, addition reaction product of cyclohexyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, butyldi-p-tolylphosphine and t-butyl-1,4-benzo Addition reaction product of quinone, addition reaction product of octyldi-p-tolylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of tricyclohexylphosphine and phenyl-1,4-benzoquinone, tributylphosphine addition reaction product of phenyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and phenyl-1,4-benzoquinone, di Addition reaction product of butylphenylphosphine and phenyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and phenyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and phenyl-1,4-benzoquinone. Discussion Addition reactant, addition reactant of butyldiphenylphosphine and phenyl-1,4-benzoquinone, addition reactant of octyldiphenylphosphine and phenyl-1,4-benzoquinone, dicyclohexyl-p-tolylphosphine and Addition reaction product of phenyl-1,4-benzoquinone, addition reaction product of dibutyl-p-tolylphosphine and phenyl-1,4-benzoquinone, dioctyl-p-tolylphosphine and phenyl-1,4-benzoquinone. Discussion Addition reaction product, addition reaction product of cyclohexyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, addition reaction product of butyldi-p-tolylphosphine and phenyl-1,4-benzoquinone, octyldi- The addition reaction product of p-tolylphosphine and phenyl-1,4-benzoquinone is preferable, and among them, the addition reaction product of tricyclohexylphosphine and t-butyl-1,4-benzoquinone, tributylphosphine and Addition reaction product of t-butyl-1,4-benzoquinone, addition reaction product of trioctylphosphine and t-butyl-1,4-benzoquinone, dicyclohexylphenylphosphine and t-butyl-1,4-benzoquinone. Discussion Addition reaction product, addition reaction product of dibutylphenylphosphine and t-butyl-1,4-benzoquinone, addition reaction product of dioctylphenylphosphine and t-butyl-1,4-benzoquinone, cyclohexyldiphenylphosphine and t-butyl-1,4-benzoquinone, addition reactant of butyldiphenylphosphine and t-butyl-1,4-benzoquinone, octyldiphenylphosphine and t-butyl-1,4-benzo. Among the addition reaction products of quinone, the addition reaction product of a phosphine compound having at least one alkyl group and a quinone compound having a t-butyl group is more preferable.

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

As a method for producing an addition reaction product of a phosphine compound in which at least one alkyl group is bonded to a phosphorus atom and a quinone compound, for example, a phosphine compound and a quinone compound that can be used as raw materials are subjected to an addition reaction in an organic solvent in which both are soluble. Afterwards, there is a method of isolation.

When the resin composition (2) contains a metallic curing accelerator as the (f2) curing accelerator, the content of the metallic curing accelerator is (a2) from the viewpoint of obtaining sufficient reactivity and curability and suppressing the curing rate from becoming too high. The mass of the solid content of the cyanate resin is preferably 1 to 200 ppm, more preferably 1 to 75 ppm, and even more preferably 1 to 50 ppm. The metal-based hardening accelerator may be mixed all at once or in multiple portions.

When the resin composition (2) contains an organic curing accelerator as the curing accelerator (f2), the content of the organic curing accelerator is (b2) from the viewpoint of obtaining sufficient reactivity and curability and from the viewpoint of suppressing the curing rate from becoming too high. The epoxy resin is preferably 0.01 to 7 parts by mass, more preferably 0.15 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and particularly preferably 0.02 to 2 parts by mass, based on 100 parts by mass of the epoxy resin in terms of solid content.

When the resin composition (2) contains a phosphorus-based curing accelerator as the curing accelerator (f2), the content is preferably 0.01 to 0.5 parts by mass, and 0.015 to 0.4 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2). It is more preferable, and 0.02 to 0.3 parts by mass is still more preferable. If the content of the phosphorus-based curing accelerator is more than the above lower limit, a sufficient curing speed is obtained, and the flatness of the resin layer on the inner layer pattern and the appearance of the interlayer insulating layer obtained by curing in the state attached to the support tend to be excellent. Moreover, if the content of the phosphorus-based curing accelerator is below the above upper limit, the handling and embedding properties of the resin film for interlayer insulating layer obtained from the resin composition (2) tend to be excellent.

<(g2) Epoxy resin hardener>

It is preferable that the resin composition (2) further contains an epoxy resin curing agent (g2).

The (g2) epoxy resin curing agent is not particularly limited, but examples thereof include those similar to the (g1) epoxy resin curing agent.

(g2) The epoxy resin curing agent may be used individually or in combination of two or more types.

Among these, the (g2) epoxy resin curing agent preferably contains at least one selected from the group consisting of an active ester curing agent and dicyandiamide.

(Activated ester hardener)

It is thought that the active ester curing agent cures by reacting with an epoxy group that has not reacted with cyanate, and the dielectric loss tangent tends to be reduced by containing the active ester curing agent.

As an active ester curing agent, compounds having a highly reactive ester group, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy ester compounds, and having a curing effect on epoxy resins can be used. You can.

The active ester curing agent may be used individually by one type, or may be used in combination of two or more types.

As the active ester curing agent, a compound having two or more active ester groups per molecule is preferred, and an aromatic compound having two or more active ester groups per molecule obtained from a compound having a polyhydric carboxylic acid and an aromatic compound having a phenolic hydroxyl group is preferred. More preferably, it is an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having two or more ester groups in a molecule of the aromatic compound is even more preferable. do. Additionally, the active ester curing agent may contain a linear or multi-branched polymer.

If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, compatibility with (a2) cyanate resin and (b2) epoxy resin can be increased, and the compound having an aromatic ring If it is a compound, heat resistance can be increased. Particularly from the viewpoint of heat resistance and the like, the active ester curing agent is preferably an active ester compound obtained from a carboxylic acid compound and a phenol compound or naphthol compound.

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

Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid.

As phenol compounds or naphthol compounds, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p- Cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzo Phenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, etc. are mentioned.

Among these, from the viewpoint of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak are preferred. And dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiphenol, and phenol novolak are more preferable, and dicyclopentadienyldiphenol and phenol novolak are more preferable, Dicyclopentadienyldiphenol is particularly preferred.

Examples of thiol compounds include benzenedithiol, triazinedithiol, and the like.

As an active ester curing agent, an active ester curing agent disclosed in Japanese Patent Application Laid-Open No. 2004-277460 may be used, or a commercial product may be used.

Commercially available active ester curing agents include those containing a dicyclopentadienyldiphenol structure, acetylates of phenol novolak, and benzoylates of phenol novolac, and among these, those containing a dicyclopentadienyldiphenol structure. It is desirable to do so. Specifically, "EXB9451", "EXB9460", "EXB9460S-65T", and "HPC-8000-65T" as containing a dicyclopentadienyldiphenol structure (above, manufactured by DIC Corporation, brand name, active group equivalent approx. 223 g/eq), “DC808” as an acetylate of phenol novolak (manufactured by Mitsubishi Chemical Corporation, active group equivalent approximately 149 g/eq), and “YLH1026” as a benzoylide of phenol novolac (manufactured by Mitsubishi Chemical Corporation) , activator equivalent weight of about 200 g/eq), etc.

The active ester curing agent can be produced by a known method. Specifically, it can be obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.

When the resin composition (2) contains an active ester curing agent, its content is determined by the resin composition ( 2) 1 to 40 parts by mass is preferable, 2 to 30 parts by mass is more preferable, 3 to 25 parts by mass is more preferable, 4 to 20 parts by mass is particularly preferable, and 5 to 15 parts by mass is particularly preferable, based on 100 parts by mass of the solid content of 2). Most desirable.

(dicyandiamide)

Dicyandiamide serves as a curing agent for (b2) epoxy resin. By containing dicyandiamide, the adhesive strength between the inner circuit pattern and the interlayer insulating layer tends to be excellent.

From the viewpoint of ease of mixing, dicyandiamide is preferably dissolved or dispersed in an organic solvent in advance and then mixed. As an organic solvent for dissolving or dispersing dicyandiamide, methylene glycol monomethyl ether, propylene glycol monomethyl ether, dimethyl acetamide, and N-methyl-2-pyrrolidone are preferable, and from the viewpoint of safety, propylene glycol monomethyl Ether is more preferred.

When the resin composition (2) contains dicyandiamide, the content is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 parts by mass, and 0.03 to 0.03 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2). 0.1 part by mass is more preferable. If the content of dicyandiamide is 0.01 parts by mass or more, the adhesive strength between the inner layer circuit pattern and the interlayer insulating layer of the present invention tends to be excellent, and if the content of dicyandiamide is 1 part by mass or less, precipitation of dicyandiamide can be suppressed.

<(h2) Resin having siloxane skeleton>

The resin composition (2) may contain a resin having a (h2) siloxane skeleton (hereinafter also referred to as “(h2) siloxane resin”).

(h2) Siloxane resin may be used individually or in combination of two or more types.

(h2) The siloxane resin is preferably a resin having a polysiloxane skeleton. Since the resin composition (2) contains the (h2) siloxane resin, when the resin composition (2) is varnished and a resin film for the interlayer insulating layer is produced, cratering, waviness, etc. do not occur on the adhesion auxiliary layer, and it is applied evenly. It becomes easier to do.

(h2) Siloxane resins include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyester-modified methylalkylpolysiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and polyether-modified polymethylalkyl. Siloxane, etc. can be mentioned.

(h2) A commercial product can be used as the siloxane resin. Commercially available (h2) siloxane resins include “BYK-310,” “BYK-313,” “BYK-300,” “BYK-320,” and “BYK-330” manufactured by Big Chemi Japan Co., Ltd. I can hear it.

When the resin composition (2) contains the (h2) siloxane resin, the content is preferably 0.005 to 1 part by mass, more preferably 0.01 to 0.8 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2), 0.02 to 0.5 parts by mass is more preferable, and 0.03 to 0.2 parts by mass is particularly preferable. (h2) If the content of the siloxane resin is 0.01 parts by mass or more, occurrence of cratering during varnish application can be suppressed, and if it is 1 part by mass or less, the illuminance is suppressed from becoming too large during desmearing, and an appropriate illuminance can be obtained. .

<(i2) phenol compound>

The resin composition (2) may further contain a phenol compound (i2). (i2) By containing a phenol compound, unreacted cyanate groups in the resulting cured product can be reduced, so moisture resistance and electrical properties tend to be excellent.

(i2) Phenol compounds may be used individually or in combination of two or more types.

(i2) The phenol compound is preferably a monofunctional phenol compound from the viewpoint of moisture resistance and electrical properties.

Examples of the monofunctional phenol compound include compounds similar to the monofunctional phenol compound described in the method for producing the cyanate prepolymer, and among these, p-(α-cumyl)phenol is preferable.

When the resin composition (2) contains the phenol compound (i2), the content is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass in terms of solid content of the resin composition (2), 0.3 to 1 part by mass is more preferable. (i2) If the content of the phenol compound is 0.1 parts by mass or more, the dielectric loss tangent can be lowered, and if the content of the phenol compound is 5 parts by mass or less, a decrease in the glass transition temperature tends to be suppressed.

The equivalent ratio (hydroxyl group/cyanate group) of the phenolic hydroxyl group of the (i2) phenolic compound and the cyanate group contained in the (a2) cyanate resin is 0.01 to 0.01 from the viewpoint of dielectric properties and moisture resistance of the resulting interlayer insulating layer. 0.3 is preferable, 0.01 to 0.2 is more preferable, and 0.01 to 0.15 is still more preferable. (i2) If the content of the phenol compound is within the above range, a sufficiently low dielectric loss tangent, especially in the high frequency band, tends to be obtained, and good moisture resistance tends to be obtained.

<Other ingredients>

The resin composition (2) may contain components other than the above components as long as they do not impair the effects of the present invention. Other components include the same components as the other components that the resin composition (1) may contain.

<Method for producing resin composition (2)>

Resin composition (2) is obtained by blending and mixing the above components. As a mixing method, a known method can be applied, for example, mixing can be done using a bead mill or the like.

The resin composition (2) may be in the form of a varnish dissolved or dispersed in the organic solvent from the viewpoint of workability when forming the resin composition layer for the interlayer insulating layer described later. After producing the varnish, the above-described dispersion treatment may be performed from the viewpoint of improving the dispersibility of the inorganic filler and the like.

The solid content concentration of the varnish can be set according to the coating device to be used. For example, when using a die coater to produce a resin composition layer with a film thickness of 35 μm after application, the solid content concentration of the varnish is 50 to 85 μm. It should be about mass%.

The resin compositions (1) and (2) of the present invention can be applied to a circuit board in the form of varnish to form an interlayer insulating layer, but can be laminated on the circuit board in the form of a sheet-like laminate material such as a resin film or prepreg. An interlayer insulating layer may be formed.

[Resin film for interlayer insulating layer]

The resin film for an interlayer insulating layer of the present invention (hereinafter also simply referred to as a “resin film”) is a resin film for an interlayer insulating layer that has a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order, and includes an adhesion auxiliary layer and an interlayer insulating layer. The resin composition layer for layers has any of the structures (i) to (iii) below.

(i) The adhesion auxiliary layer is a layer containing the resin composition (1) of the present invention.

(ii) The resin composition layer for the interlayer insulating layer is a layer containing the resin composition (2) of the present invention.

(iii) The adhesion auxiliary layer is a layer containing the resin composition (1) of the present invention, and the resin composition layer for interlayer insulating layer is a layer containing the resin composition (2) of the present invention.

The resin film for an interlayer insulating layer of the present invention is suitable for a build-up type multilayer printed wiring board, and by using the resin film for an interlayer insulating layer of the present invention, a conductor layer with high adhesive strength can be formed on a smooth interlayer insulating layer. there is. In addition, in the present invention, “smooth” means that the surface roughness (Ra) is less than 0.3 μm. In addition, the surface roughness (Ra) in the present invention can be measured using, for example, a non-contact surface roughness meter "wykoNT9100" (Brooker AXS Co., Ltd., brand name).

In addition, there is no clear interface between the adhesion auxiliary layer and the resin composition layer for the interlayer insulating layer, and for example, a part of the components of the adhesion auxiliary layer may be in a state of flowing in the resin composition layer for the interlayer insulating layer.

The thickness of the resin film of the present invention can be determined by the thickness of the conductor layer formed on the printed wiring board, but since the thickness of the conductor layer is usually 5 to 70 μm, it is preferably 15 to 120 μm, and multilayer printing From the viewpoint of enabling thinning of the wiring board, the thickness is more than that of the conductor layer, and 20 to 90 μm is more preferable, and 25 to 60 μm is still more preferable.

<Resin composition layer for interlayer insulating layer>

The resin composition layer for the interlayer insulating layer is a layer provided between the circuit board and the adhesion auxiliary layer when manufacturing a multilayer printed wiring board using the resin film of the present invention. Additionally, when there are through holes, via holes, etc. in the circuit board, the resin composition layer for the interlayer insulating layer flows among them and also plays a role of filling the holes.

The resin composition layer for the interlayer insulating layer is preferably obtained by forming a layer of the resin composition (2) of the present invention. Layer formation can be performed, for example, by dissolving and/or dispersing the resin composition (2) of the present invention in the organic solvent to form a varnish, followed by applying and drying.

The thickness of the resin composition layer for the interlayer insulating layer is preferably greater than or equal to the thickness of the conductor layer of the circuit board on which the resulting resin film is laminated. The thickness of the conductor layer of the circuit board is usually 5 to 70 μm, so 10 to 100 μm is preferable, and from the viewpoint of enabling thinning of the multilayer printed wiring board, it has a thickness of 15 to 80 μm or more than the conductor layer. ㎛ is more preferable, and 20 to 50 ㎛ is more preferable.

<Adhesion auxiliary layer>

The adhesion auxiliary layer is a layer that insulates the multilayered circuit patterns from each other in a multilayer printed wiring board multilayered by the build-up method, and also serves to increase the plating peeling strength by smoothing the circuit patterns.

The adhesion auxiliary layer is preferably obtained by layer forming the resin composition (1) of the present invention. Layer formation can be performed, for example, by dissolving and/or dispersing the resin composition (1) of the present invention in the organic solvent to form a varnish, followed by applying and drying.

The thickness of the adhesion auxiliary layer is preferably 1 to 15 μm, more preferably 1 to 10 μm, from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, 2 to 8 μm is more preferable, and 2 to 7 μm is particularly preferable.

<Support>

Examples of the support include organic resin films, metal foils, and release papers.

Materials for 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; Polycarbonate, polyimide, etc. can be mentioned. Among these, PET is preferable from the viewpoint of price and handleability.

Examples of metal foil include copper foil and aluminum foil. When copper foil is used for the support, a circuit can also be formed using the copper foil as a conductor layer. Examples of copper foil include rolled copper and electrolytic copper foil. The thickness of the copper foil is, for example, 2 to 36 μm. When using thin copper foil, you may use copper foil with a carrier from the viewpoint of improving workability.

These supports and the protective film described later may be subjected to surface treatment such as release treatment, plasma treatment, or corona treatment. Examples of the mold release agent used in the mold release treatment include silicone resin mold release agents, alkyd resin mold release agents, and fluororesin mold release agents.

From the viewpoint of handling and economic efficiency, the thickness of the support is preferably 10 to 120 μm, more preferably 15 to 80 μm, and even more preferably 25 to 50 μm. If the thickness of the support is 10 μm or more, handling becomes easy. On the other hand, since the support body is usually ultimately peeled off or removed when manufacturing a multilayer printed wiring board, it is preferable to have a thickness of 120 μm or less from the viewpoint of energy saving and the like.

<Protective film>

The resin film of the present invention may have a protective film. The protective film is installed on the surface opposite to the surface on which the support of the resin film of the present invention is installed, and is used for the purpose of preventing adhesion of foreign substances, etc. to the resin film and occurrence of scratches. The protective film can be peeled off before laminating the resin film of the present invention on a circuit board, etc. by laminating, heat pressing, etc.

Examples of the protective film include the same material as the support. The thickness of the protective film is, for example, 1 to 40 μm.

The protective film is peeled off before laminating the resin film of the present invention on a circuit board, etc. by laminating, heat pressing, etc.

<Method for producing resin film>

The resin film of the present invention, for example, is made by applying the resin composition (1) of the present invention in the form of varnish on a support, drying it, forming an adhesion auxiliary layer on the support, and then applying varnish on the adhesion auxiliary layer. It can be manufactured by applying a varnish of the resin composition (2) of the present invention in the state and then drying it to form a resin composition layer for an interlayer insulating layer.

As another method, for example, an adhesion auxiliary layer is formed on the support by the method described above, and separately, a resin composition layer for an interlayer insulating layer is formed on a peelable film, and the adhesion auxiliary layer formed on the support and the interlayer insulation formed on the film are formed. A method of laminating the layer resin composition layer so that the surface on which the adhesion auxiliary layer is formed and the surface on which the interlayer insulating layer resin composition layer is formed are in contact, etc. can also be mentioned. In this case, the film from which the resin composition layer for interlayer insulating layer can be peeled can also serve as a protective film for the resin film.

As a method of applying the resin composition of the present invention, a method of applying using a known coating device such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, or die coater can be applied. The coating device may be appropriately selected depending on the target film thickness.

As drying conditions after applying the resin composition of the present invention, for example, it is preferable to dry so that the content of the organic solvent in the resulting resin film is 10 mass% or less, and it is more preferable to dry it so that it is 5 mass% or less. do.

Drying conditions also vary depending on the amount and type of organic solvent in the varnish. For example, if the varnish contains 20 to 80% by mass of an organic solvent, drying may be performed at 50 to 150°C for about 1 to 10 minutes. As for drying conditions, it is desirable to establish timely and desirable drying conditions through simple experiments.

The area of the resin composition layer for the adhesion auxiliary layer and the interlayer insulating layer is preferably smaller than the area of the support from the viewpoint of handling.

Additionally, the resin film can be wound into a roll and stored. In this case, the width of the resin composition layer for the adhesion auxiliary layer and the interlayer insulating layer is preferably smaller than the width of the support from the viewpoint of handling.

[Multilayer printed wiring board]

The multilayer printed wiring board of the present invention contains a cured product of the resin composition of the present invention or the resin film for an interlayer insulating layer.

The multilayer printed wiring board of the present invention can be manufactured, for example, by laminating the resin film of the present invention to a circuit board. Specifically, it can be manufactured by a manufacturing method including the following steps (1) to (6) (however, step (3) is optional), and after steps (1), (2) or (3), The support may be peeled off or removed.

(1) A process of laminating the resin film of the present invention on one side or both sides of a circuit board (hereinafter referred to as the laminate process (1)).

(2) A process of thermosetting the laminated resin film to form an insulating layer (hereinafter referred to as the insulating layer forming process (2)).

(3) A process of punching the circuit board on which the insulating layer has been formed (hereinafter referred to as the punching process (3)).

(4) A process of roughening the surface of the insulating layer with an oxidizing agent (hereinafter referred to as the roughening treatment process (4)).

(5) A process of forming a conductor layer on the surface of the roughened insulating layer by plating (hereinafter referred to as the conductor layer formation process (5)).

(6) Process of forming a circuit in the conductor layer (hereinafter referred to as circuit formation process (6)).

The laminating process (1) is a process of laminating the resin film of the present invention on one side or both sides of a circuit board using a vacuum laminator. As the vacuum laminator, a commercially available vacuum laminator can be used. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Kasey Co., Ltd., and Hitachi Kasei Co., Ltd. A vacuum laminator made by Electronics Co., Ltd., etc. can be mentioned.

When a protective film is provided on the resin film, the protective film is peeled off or removed, and then laminated by pressing and heating the resin composition layer for the interlayer insulating layer of the resin film to the circuit board so that it is in contact with the circuit board. .

For the laminate, for example, the resin film and the circuit board are preheated (preheated) as necessary, then the pressing temperature (lamination temperature) is set to 60 to 140°C and the pressing pressure is set to 0.1 to 1.1 MPa (9.8×10 4 to 9.8×10 ⁴ ). It can be performed under reduced pressure of 107.9×10 ⁴ N/m2) and air pressure of 20mmHg (26.7hPa) or less. Additionally, the lamination method may be a batch method or a continuous method using a roll.

In the insulating layer formation process (2), first, the resin film laminated to the circuit board in the lamination process (1) is cooled to around room temperature.

In the case of peeling off the support, after peeling, the resin film laminated to the circuit board is heat-cured to form an insulating layer, that is, an insulating layer that later becomes an “interlayer insulating layer.”

The conditions for heat curing can be selected from the range of 100 to 200°C for 5 to 30 minutes in the first stage, and from 20 to 80 minutes at 140 to 220°C for the second stage. When a support that has been subjected to a mold release treatment is used, the support may be peeled off after heat curing.

After forming the insulating layer by the above method, a punching process (3) may be performed if necessary. The punching process (3) is a process of forming via holes, through holes, etc. by punching the circuit board and the formed insulating layer using methods such as drill, laser, plasma, or a combination thereof. As lasers, carbon dioxide gas lasers, YAG lasers, UV lasers, excimer lasers, etc. are used.

In the roughening treatment step (4), the surface of the insulating layer is roughened with an oxidizing agent. Additionally, when via holes, through holes, etc. are formed in the insulating layer and the circuit board, the so-called "smear" generated when forming these may be removed with an oxidizing agent. Roughening treatment and removal of smear can be performed simultaneously.

Examples of oxidizing agents include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide, sulfuric acid, and nitric acid. Among these, alkaline permanganate solution (for example, potassium permanganate, sodium hydroxide aqueous solution of sodium permanganate), which is a widely used oxidizing agent for roughening the insulating layer in the production of multilayer printed wiring boards by the build-up method, can be used. .

Through the roughening treatment, uneven anchors are formed on the surface of the insulating layer.

In the conductor layer forming step (5), a conductor layer is formed by plating on the surface of the insulating layer that has been roughened and has irregular anchors formed.

Examples of the plating method include electroless plating and electrolytic plating. The metal for plating is not particularly limited as long as it is a metal that can be used for plating, and includes copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and at least one of these metal elements. and alloys containing species. Among these, copper and nickel are preferable, and copper is more preferable.

Additionally, a method of first forming a plating resist with a reverse pattern to that of the conductor layer (wiring pattern) and then forming the conductor layer (wiring pattern) only by electroless plating can also be adopted.

After forming the conductor layer, annealing treatment may be performed at 150 to 200°C for 20 to 120 minutes. By performing annealing treatment, the adhesive strength between the interlayer insulating layer and the conductor layer tends to be further improved and stabilized. Additionally, hardening of the interlayer insulating layer may be advanced through this annealing treatment.

In the circuit formation process (6), methods for pattern processing the conductor layer and forming the circuit include, for example, the subtractive method, the full additive method, the semi-additive process (SAP), and the modified semi-additive method. Known methods such as the additive method (m-SAP: modified Semi Additive Process) can be used.

The surface of the conductor layer produced in this way may be roughened. By roughening the surface of the conductor layer, adhesion to the resin in contact with the conductor layer tends to improve. To roughen the conductor layer, organic acid-based microetchants such as "CZ-8100," "CZ-8101," and "CZ-5480" (all manufactured by Mack Co., Ltd., brand names) can be used.

The circuit board used in the multilayer printed wiring board of the present invention is, for example, on one or both sides of a substrate such as glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, or thermosetting polyphenylene ether substrate, One example is one in which a pattern-processed conductor layer (circuit) is formed.

From the viewpoint of the adhesion of the interlayer insulating layer to the circuit board, the surface of the conductor layer of the circuit board may be roughened in advance, such as by blackening treatment.

[Prepreg]

The resin composition of the present invention can also be applied to prepreg.

As a preferred form of applying the resin composition of the present invention to a prepreg, a prepreg (hereinafter referred to as “ Also referred to as “prepreg with adhesion auxiliary layer”). Hereinafter, the mode will be described.

<Resin composition layer for interlayer insulating layer containing fiber substrate>

The resin composition layer for an interlayer insulating layer containing a fiber base is obtained, for example, by impregnating the fiber base with the resin composition (2) of the present invention and drying it.

Methods for impregnating the resin composition (2) into the fiber substrate include a hot melt method, a solvent method, and the like.

The hot melt method is a method of coating a resin composition on coated paper with excellent peelability from the resin composition without dissolving the resin composition in an organic solvent and laminating it on a fiber base, or a method of coating the resin composition on coated paper with excellent peelability from the resin composition and laminating it on a fiber base, or without dissolving the resin composition in an organic solvent. , This is a method of directly applying it to a sheet-like reinforcing base material using a die coater or the like.

The solvent method is a method of dissolving a resin composition in an organic solvent to produce a varnish and impregnating the fiber base material with this varnish.

As drying conditions after impregnation, for example, heat drying at a temperature of 80 to 180°C for 1 to 10 minutes and semi-curing (B staging) can be used to obtain a resin composition layer for an interlayer insulating layer containing a fiber base.

As a fiber base material, for example, a well-known material used in various laminates for electrical insulating materials can be used.

Materials for the fiber base include inorganic fibers such as E glass, D glass, S glass, and Q glass; Organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. In applications other than electrical insulating materials, it is also possible to use, for example, carbon fibers used in fiber-reinforced substrates.

Shapes of the fiber base include woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat.

The material and shape of the fiber base material may be selected depending on the use, performance, etc. of the prepreg, and if necessary, two or more types of materials and shapes may be combined.

The thickness of the fiber base material can be, for example, 0.03 to 0.5 mm.

From the viewpoint of heat resistance, moisture resistance, and processability, the fiber base material can be one that has been surface treated with a silane coupling agent or the like, or one that has been subjected to a mechanical opening treatment.

<Adhesion auxiliary layer>

The adhesion auxiliary layer in the prepreg with an adhesion auxiliary layer contains the resin composition (1) of the present invention.

The thickness of the adhesion auxiliary layer is preferably 1 to 15 μm, more preferably 1 to 10 μm, from the viewpoint of obtaining an interlayer insulating layer with low surface roughness and excellent adhesive strength of the conductor layer formed by the plating method, and 1 to 15 μm. to 7㎛ is more preferable.

<Method for manufacturing prepreg with adhesive auxiliary layer>

The prepreg with an adhesion auxiliary layer can be manufactured, for example, by forming an adhesion auxiliary layer on the resin composition layer for an interlayer insulating layer containing the above fiber base material. As a method of forming an adhesion auxiliary layer, for example, in the resin film of the present invention described above, a method of forming an adhesion auxiliary layer on the resin composition layer for an interlayer insulating layer can be applied.

Next, an example of a method for manufacturing a multilayer printed wiring board using prepreg with an adhesion auxiliary layer will be described.

One or more sheets of prepreg with an adhesion auxiliary layer are stacked on a circuit board, sandwiched between metal plates with a release film interposed therebetween, and laminated by vacuum pressing under pressure and heating conditions. When stacking multiple prepregs, it is preferable to stack them so that an adhesion auxiliary layer is formed on the outside. Pressurizing and heating conditions can be, for example, press lamination at a pressure of 5 to 40 kgf/cm2 and a temperature of 120 to 200°C for 20 to 100 minutes.

In addition, similarly to the resin film of the present invention, the prepreg with an adhesion auxiliary layer may be laminated to a circuit board by a vacuum lamination method and then heat-cured. Thereafter, the surface of the cured prepreg is roughened by the same method as the method described in the section on the multilayer printed wiring board of the present invention, and then a conductor layer is formed, thereby producing a multilayer printed wiring board.

[Semiconductor package]

The present invention also provides a semiconductor package formed by mounting a semiconductor element on the multilayer printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the multilayer printed wiring board of the present invention and sealing the semiconductor element with a sealing resin or the like.

Example

[1] Next, the first invention will be explained in more detail by way of examples, but the first invention is not limited at all by these examples.

Example 1

As the epoxy resin, 25.8 parts by mass of "NC-3000-H" (Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass), which is a biphenyl novolac type epoxy resin,

As a novolak-type phenolic resin, 6.3 parts by mass of "PAPS-PN2" (manufactured by Asahi Yukizai Kogyo Co., Ltd., brand name, solid concentration 100% by mass, Mw/Mn = 1.17),

As an epoxy resin curing agent, 4.9 parts by mass of "LA-1356-60M" (manufactured by DIC Corporation, brand name, solvent: MEK, solid concentration 60% by mass), which is a triazine-modified phenol novolak resin,

As an inorganic filler, the surface of “SO-C2” (manufactured by Admatex Co., Ltd., brand name, average particle size: 0.5 μm) was treated with an aminosilane coupling agent, and silica (solid concentration: 70% by mass) dispersed in MEK was added. ) to 92.9 parts by mass,

As a curing accelerator, 0.026 parts by mass of 2-ethyl-4-methylimidazole, "2E4MZ" (manufactured by Shikoku Chemical Industry Co., Ltd., brand name, solid content concentration 100% by mass),

13.1 parts by mass of MEK was added as an additional solvent, and mixing and bead mill dispersion treatment were performed to produce the resin composition varnish 1 for adhesive film.

The resin composition varnish 1 for adhesive film obtained above was applied onto the support film PET (Teijin DuPont Film Co., Ltd., brand name: G2, film thickness: 50 μm), and then dried to form a resin composition layer. . In addition, the coating thickness was 40 μm, and drying was performed so that the residual solvent in the resin composition layer was 8.0 mass%. After drying, a polyethylene film (manufactured by Tamapoly Co., Ltd., brand name: NF-13, thickness: 25 μm) was laminated as a protective film on the resin composition layer side. After that, the obtained film was wound into a roll to obtain adhesive film 1.

Examples 2 to 6, 8, Comparative Examples 1 to 4

Adhesive films 2 to 6 and 8 to 12 were obtained in the same manner as in Example 1, except that the raw material composition and manufacturing conditions were changed as shown in Table 1.

Example 7

Resin varnish A prepared in the following procedure was applied and dried on a support film, PET (Teijin Dupont Film Co., Ltd., product name: G2, film thickness: 50 μm) to a film thickness of 10 μm, resulting in a thickness of 60 μm. A thick support film 2 was prepared.

The resin varnish A used above was produced according to the following procedures.

As the epoxy resin, 63.9 parts by mass of "NC-3000-H" (Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass), which is a biphenyl novolac type epoxy resin,

As an epoxy resin curing agent, 18.0 parts by mass of "LA-1356-60M" (DIC Co., Ltd., brand name, solvent; MEK, solid concentration 60% by mass), which is a triazine-modified phenol novolak resin,

15.2 parts by mass of “EXL-2655” (trade name, manufactured by Rohm & Haas Electronics Co., Ltd.), which is a core-shell rubber particle,

As an inorganic filler, 8.8 parts by mass of fumed silica "Aerosil R972" (manufactured by Nippon Aerosil Co., Ltd., brand name, average particle size; 0.02 μm, solid content concentration 100% by mass),

As a curing accelerator, 1.28 parts by mass of 2-ethyl-4-methylimidazole, "2E4MZ" (manufactured by Shikoku Chemical Industry Co., Ltd., brand name, solid content concentration 100% by mass),

As an additional solvent, 226.1 parts by mass of cyclohexanone was blended, and mixing and bead mill dispersion treatment were performed to produce resin varnish A.

The resin varnish A obtained above was applied to a film thickness of 10 ㎛ on PET (Teijin DuPont Film Co., Ltd., product name: G2, film thickness: 50 ㎛) as a support film, and then dried to obtain a film thickness of 10 ㎛. Support film 2 of 60 μm was obtained.

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

Adhesive film 7 was obtained in the same manner as in Example 1, using support film 2 and a resin composition varnish for adhesive films.

[Assessment Methods]

The obtained adhesive films 1 to 12 were evaluated by the following method.

(Production and test method of samples for handling adhesive film test)

The obtained adhesive films 1 to 12 were cut to a size of 500 mm x 500 mm, and samples 1 to 12 for testing the handleability of the adhesive film were produced.

Using samples 1 to 12 for the handling test of the produced adhesive film, the handling was evaluated by the following methods (1) to (3), and those that were defective in any test were considered “poor handling” in any test. Those that were not defective were rated as “good handleability.”

(1) For samples 1 to 12 for the handling test of the adhesive film, the protective film was first peeled off. When peeling off the protective film, part of the applied and dried resin adhered to the protective film side, or powder falling occurred, which was considered poor handling.

(2) There were two points at the center of the film (two points at the ends to make 500 mm x 250 mm), and cracks in the applied and dried resin were considered poor handling.

(3) Placed on “MCL-E-679FG(R)”, a copper clad laminate in which the copper foil on the surface was subjected to blackening and reduction treatment (manufactured by Hitachi Kasei Co., Ltd., copper foil thickness 12 μm, plate thickness 0.41 mm). Lamination was performed by lamination using a vacuum pressurized laminator "MVL-500" (made by Meiki Seisakusho Co., Ltd., brand name). At this time, the vacuum degree was set to 30 mmHg or less, the temperature was set to 90°C, and the pressure was set to 0.5 MPa. After cooling to room temperature, the support film was peeled (for adhesive film 7, the support film 2 was peeled between PET and the resin layer formed thereon). At this time, powder falling occurred or the PET was torn along the way, resulting in poor handling properties.

(Production and testing method of samples for measuring thermal expansion coefficient)

The obtained adhesive films 1 to 12 were cut to a size of 200 mm It was laminated by using (Shoje, brand name). At this time, the vacuum degree was set to 30 mmHg or less, the temperature was set to 90°C, and the pressure was set to 0.5 MPa.

After cooling to room temperature, the support film was peeled off (for adhesive film 7, it was peeled between PET and the resin layer formed thereon in support film 2) and cured in a dryer at 180°C for 120 minutes. After that, the copper foil was removed with a ferric chloride solution, and the pieces cut to a width of 3 mm and a length of 8 mm were used as samples 1 to 12 for measuring the thermal expansion coefficient.

Using the produced samples 1 to 12 for thermal expansion coefficient measurement, the thermal expansion coefficient was measured by the following method.

The obtained samples 1 to 12 for measuring thermal expansion coefficient were heated to 240°C at a temperature increase rate of 10°C/min using a thermomechanical analysis device manufactured by Seiko Instruments Co., Ltd., and cooled to -10°C, then heated at a temperature increase rate of 10°C/min. A change curve of the expansion amount when the temperature was raised to 300°C per minute was obtained, and the average coefficient of thermal expansion from 0 to 150°C was obtained from the change curve of the expansion amount.

(Manufacturing and testing method of embeddedness evaluation board)

The inner layer circuit used for the embeddedness evaluation board is as follows. “MCL-E-679FG(R)” (made by Hitachi Kasei Co., Ltd., brand name), a copper-clad laminate with a copper foil thickness of 12㎛ and a sheet thickness of 0.15mm (including the copper foil thickness), has a diameter of 0.15mm. Through holes were manufactured by drill punching to form a group of 25 x 25 at 5 mm intervals. Next, desmear and electroless plating were performed, and electrolytic plating was performed in the through hole using electrolytic plating.

As a result, a circuit board was obtained with a plate thickness of 0.2 mm including the copper thickness, a diameter of 0.1 mm, and 25 x 25 through holes spaced at 5 mm intervals.

Next, the adhesive films 1 to 12 from which the protective film has been peeled are placed so that the resin composition layer faces the circuit surface side of the circuit board, and then placed in a batch-type vacuum laminator “MVL-500” (manufactured by Meiki Seisakusho Co., Ltd.) It was laminated using (trade name). At this time, the vacuum degree was set to 30 mmHg, the temperature was set to 90°C, and the pressure was set to 0.5 MPa.

After cooling to room temperature, the circuit board having through holes with adhesive films on both sides was sandwiched between two aluminum plates with a thickness of 1 mm, and lamination was performed using the vacuum laminator. At this time, the vacuum degree was set to 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 was peeled off (for adhesive film 7, it was peeled between PET and the resin layer formed thereon in support film 2) and cured in a dryer at 180°C for 120 minutes. In this way, embedding evaluation substrates 1 to 12 were obtained.

Using the produced embedding evaluation substrates 1 to 12, embedding was evaluated by the following method.

Using a contact-type surface roughness meter "SV2100" (brand name) manufactured by Mitsutoyo Corporation, the level difference on the surface of the through-hole portion of the embedding evaluation substrates 1 to 12 was measured. The step difference was measured so that 10 surface center portions of the through hole were included, and the average value of the 10 concave portions was calculated.

[Table 1]

The components in Table 1 are shown below.

[Epoxy Resin]

NC-3000-H: Biphenyl novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass)

・N673-80M: Cresol novolac type epoxy resin (manufactured by DIC Corporation, brand name, solvent; MEK, solid concentration 80% by mass)

[Novolak-type phenol resin]

PAPS-PN2: Novolac type phenolic resin (manufactured by Asahi Yukizai Kogyo Co., Ltd., brand name, solid content concentration 100% by mass, Mw/Mn=1.17)

PAPS-PN3: Novolac type phenol resin (manufactured by Asahi Yukizai Kogyo Co., Ltd., brand name, solid content concentration 100% by mass, Mw/Mn=1.50)

HP-850: Novolak-type phenol resin manufactured using hydrochloric acid rather than phosphoric acid (manufactured by Hitachi Kasei Co., Ltd., brand name, solid content concentration 100% by mass)

[Triazine modified phenol novolac resin]

LA-1356-60M: Triazine-modified phenol novolac resin (manufactured by DIC Corporation, brand name, solvent; MEK, solid content concentration 60% by mass)

[Inorganic filler]

SO-C2: The surface of silica “SO-C2” (brand name, average particle size; 0.5 μm) manufactured by Admatex Co., Ltd. was treated with an aminosilane coupling agent, and the silica dispersed in MEK solvent (solid content concentration) 70% by mass)

SO-C6: The surface of silica “SO-C6” (brand name, average particle size; 2.2 μm) manufactured by Admatex Co., Ltd. was treated with an aminosilane coupling agent, and the silica dispersed in MEK solvent (solid content concentration) 70% by mass)

Aerosil R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., brand name, solid content concentration 100 mass%, specific surface area: 100 m2/g)

[Curing accelerator]

2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., brand name, solid concentration 100% by mass)

From Table 1, it can be seen that the adhesive film of the present invention has good handling properties, and that an interlayer insulating layer with 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 was not used, any of the handling properties, thermal expansion coefficients, and embedding properties were poor.

That is, it can be seen that according to the first invention, it is possible to provide an adhesive film with a low coefficient of thermal expansion, excellent embedding properties, and excellent handling properties, and an interlayer insulating layer with a low coefficient of thermal expansion after curing.

[2] Next, the second invention will be described in more detail with reference examples, but the second invention is not limited at all by these examples.

In addition, the values in each table are the mass part of the solid content, and in the case of a solution or dispersion, it is the solid content conversion amount.

The weight average molecular weight and number average molecular weight of the cyanate prepolymer and polyamide resin were determined by gel permeation chromatography (GPC) by conversion from a calibration curve using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene: TSKgel (SuperHZ2000, SuperHZ3000 (manufactured by Tosoh Corporation)). The conditions of GPC are shown below.

·Device: Pump: 880-PU [made by Nippon Bunko Co., Ltd.]

RI detector: 830-RI [Nippon Bunko Co., Ltd.]

Constant temperature bath: 860-CO [Nippon Bunko Co., Ltd.]

Autosampler: AS-8020 [made by Tosoh Corporation]

·Eluent: Tetrahydrofuran

·Sample concentration: 30mg/5mL

·Injection volume: 20μL

·Flow rate: 1.00mL/min

·Measurement temperature: 40℃

[2-1] Reference example A

The evaluation method and evaluation results of Reference Example A regarding the resin composition (1) of the present invention will be explained.

[Evaluation method in reference example A]

<Cutting evaluation>

The resin film and prepreg obtained in each example were stored in a storage room at 5°C for one week, taken out from the refrigerator, left at room temperature (23°C) for 2 hours, and then cut into a size of 400 mm x 300 mm using a cutter.

The case where powder falling from the end of the PET film was observed when cutting the resin film and prepreg, or where cracks occurred during handling was designated as “B”, and the case where powder falling was not observed and no cracks occurred was designated as “B”. It was set as “A”. The cutting evaluation can be used as an indicator of the storage stability of the resin film or prepreg, and the storage stability is excellent when no powder fall is observed and no cracks occur.

<Irregularities on the surface of the interlayer insulation layer>

The resin film and prepreg obtained in each example were cut to a size of 400 mm x 300 mm and laminated on a printed wiring board on which a wiring pattern was formed. In addition, the resin film is laminated after being placed so that the resin composition layer for the interlayer insulating layer faces the circuit surface of the printed wiring board, and the prepreg is prepared by peeling off the release PET film and then using the resin for the interlayer insulating layer containing glass fiber. After the composition layer was arranged to face the circuit surface of the printed wiring board, lamination was performed.

The laminating device was performed using a vacuum pressurized laminator "MVLP-500/600IIA" (made by Meiki Seisakusho Co., Ltd., brand name), and after vacuuming at 100°C for 30 seconds, pressure was applied at 0.5 MPa for 30 seconds. After that, hot pressing was performed at 100°C for 60 seconds and 0.5 MPa.

In addition, the printed wiring board on which the wiring pattern was formed was formed on a copper clad laminate "MCL-E-679FG" (made by Hitachi Kasei Co., Ltd., brand name) having a copper layer with a thickness of 35 ㎛ by the subtractive method, and the line/space was 165. A set of 15 ㎛/165 ㎛ wires was used.

Next, the printed wiring board on which the resin film was laminated was cooled to room temperature, the PET film as a support was peeled off, and curing was performed in an explosion-proof dryer at 170°C for 40 minutes to produce a substrate for evaluating the embedding of the wiring pattern.

The embeddedness of the wiring pattern was evaluated based on the size of the irregularities on the surface of the interlayer insulating layer of the manufactured wiring pattern embeddedness evaluation board. The size of the unevenness was measured using a stylus-type evaluation type surface roughness measuring instrument “Surf Test SV-2100” (manufactured by Mitsutoyo Corporation, brand name), and the average value of n = 10 was calculated. The smaller the irregularities on the surface of the interlayer insulating layer, the better the embedding properties of the wiring pattern. In this specification, it is practically preferable that the average value of the irregularities is less than 3 μm, and more preferably less than 2 μm.

<Laser processability>

The embeddedness evaluation board of the wiring pattern produced above was used, and via holes for interlayer connection were formed in locations where an interlayer insulating layer was required. The via hole was formed using a carbon dioxide laser processing machine (LCO-1B21 type) under the conditions of a beam diameter of 60 μm, a frequency of 500 Hz, a pulse width of 5 μs, and a number of shots of 2, to produce a laser processability evaluation board. Laser processability was evaluated by observing the surface of the via portion of the laser processing portion of the substrate and observing the cross-sectional shape of some vias.

Observation was carried out using a scanning electron microscope (SEM) "S-4700" (trade name, manufactured by Hitachi Seisakusho Co., Ltd.), and scattering of resin or distorted via shapes were observed during surface observation. B" was set, and the one in which no scattering of resin was observed and the distorted via shape was not seen during surface observation was set to "A".

<Surface roughness (Ra)>

A part of the laser processability evaluation substrate obtained above was used as a test piece, and roughening was performed according to the following procedure.

The test piece was immersed in a swelling liquid "CIRCUPOSIT MLB CONDITIONER211" (manufactured by Rohm & Haas Electronics Co., Ltd.) heated to 80°C for 3 minutes. Next, it was immersed in a cotton roughening liquid "CIRCUPOSIT MLB PROMOTER213" (produced by Rohm & Haas Electronics Co., Ltd.) heated to 80°C for 8 minutes. Subsequently, it was neutralized by immersing it in a neutralizing liquid “CIRCUPOSIT MLB NEUTRALIZER MLB216” (manufactured by Rohm & Haas Electronics Co., Ltd.) heated to 45°C for 5 minutes. In this way, a substrate for surface roughness measurement in which the surface of the interlayer insulating layer was roughened was obtained.

For the obtained substrate for surface roughness measurement, the surface roughness of the interlayer insulating layer was measured using a non-contact surface roughness meter "wykoNT9100" (Brooker AXS Co., Ltd., brand name), using an internal lens 1x and an external lens 50x. was performed to obtain the arithmetic average roughness (Ra). The arithmetic average roughness (Ra) was determined by measuring the average roughness of five locations on a random portion of the surface roughness measurement substrate (however, an area where a via hole is not formed by a laser), and taking the average value thereof. From the point of view of the present invention, the arithmetic mean roughness (Ra) is preferably smaller, and less than 200 nm is practically preferable.

<Peel strength>

Using a part of the surface roughness measurement substrate obtained above as a test piece, a substrate for measuring the adhesive strength (peel strength) of the interlayer insulating layer and the conductor layer (copper layer) was produced in the following procedure.

First, the test piece was treated with an alkaline cleaner at 60°C, “Cleaner Securigant 902” (Atotech Japan Co., Ltd., brand name) for 5 minutes and degreased. After washing, it was treated with "Predip Neogant B" (Atotech Japan Co., Ltd., brand name), a predip solution at 23°C, for 2 minutes. After that, treatment was performed for 5 minutes with “Activator Neogant 834” (trade name, manufactured by Atotech Japan Co., Ltd.), which is an activator liquid at 40°C, to cause the palladium catalyst to adhere. Next, it was treated with “Reducer Neogant WA” (Atotech Japan Co., Ltd., brand name), a reducing solution at 30°C, for 5 minutes. Next, a chemical copper solution [“Basic Printogant MSK-DK”, “Copper Solution Printogant MSK”, “Stabilizer Printogant MSK”] (all manufactured by Atotech Japan Co., Ltd., brand name) was added, and the plating thickness was 0.5 μm. Electroless plating was performed until the thickness was reached. After electroless plating, a bake treatment was performed at 120°C for 15 minutes to relieve the stress remaining in the plating film and to remove remaining hydrogen gas.

Next, electrolytic plating was performed on the electroless plated substrate so that the plating thickness was about 30 μm. After electrolytic plating, it was cured by heating at 190°C for 90 minutes.

A 10 mm wide resist was formed on the copper layer of the substrate obtained above, and the copper layer other than the resist formed portion was removed by etching with ferric chloride to prepare a peel strength measurement substrate having a 10 mm wide copper layer as the peel measurement portion. got it

One end of the peel measurement portion of the obtained peel strength measurement substrate was peeled from the interface between the copper layer and the interlayer insulating layer, held with a gripping tool, and the load when peeled off in the vertical direction at room temperature at a tensile speed of 50 mm/min was measured.

<Thermal expansion coefficient>

The resin film and prepreg obtained in each example were laminated to the roughened surface of copper foil "YGP-12" (product name, manufactured by Nippon Denkai Co., Ltd.) under the same conditions as the manufacturing method of the wiring pattern embedding evaluation board. . In addition, the resin film is disposed so that the resin composition layer for the interlayer insulating layer faces the roughened surface of the copper foil, and the prepreg is arranged so that the resin composition layer for the interlayer insulating layer containing glass fiber is placed on the copper foil after peeling off the release PET film. After being arranged to face the roughening screen, lamination was performed.

Subsequently, after cooling to room temperature, the PET film as a support was peeled off. After that, it was cured at 170°C for 40 minutes in an explosion-proof dryer, and then further heat-cured at 190°C for 90 minutes. From the obtained film with copper foil, the copper foil was removed by etching with an ammonium persulfate solution. Next, after washing with water, it was dried at 80°C for 10 minutes and cut into pieces with a width of 3 mm and a length of 8 mm, which were used as samples for measuring the thermal expansion coefficient.

The obtained sample for thermal expansion coefficient measurement was heated to 240°C at a temperature increase rate of 10°C/min using a thermomechanical analysis device “SI5000” manufactured by Seiko Instruments Co., Ltd., and cooled to -10°C, then heated to a temperature increase rate of 10°C/min. A change curve of the expansion amount when the temperature was raised to 300°C per minute was obtained, and the average coefficient of thermal expansion from 0 to 150°C was obtained from the change curve of the expansion amount.

<Dielectric loss tangent>

Samples for dielectric loss tangent measurement were produced using the resin films and prepregs obtained in each example. First, a resin film or prepreg was laminated on the glossy surface of copper foil (electrolytic copper foil, thickness 12 μm). The lamination was performed using the same equipment and conditions as the manufacturing method for the wiring pattern embedding evaluation board. After lamination, it was cooled to room temperature, and the PET film as a support was peeled off.

Next, the same resin film or prepreg was further laminated on the resin film or prepreg laminated on the copper foil under the same conditions, and after cooling, the PET film as a support was peeled off in the same manner. For the resin film, this operation was repeated 5 times, and a laminated product of a resin film or prepreg with a total thickness of 200 μm was produced, respectively. Next, the PET film as a support was peeled off from each laminated product, and then heat-cured at 190°C for 90 minutes. Subsequently, the copper foil was removed using a copper etching solution of ferric chloride, and a sheet-shaped resin plate with a thickness of 200 μm was obtained.

The obtained resin plate was cut into test pieces with a width of 2 mm and a length of 70 mm, and the dielectric loss tangent was measured using a network analyzer (manufactured by Agilent Technologies, Ltd., brand name: E8364B) and a 5GHz-compatible cavity resonator. The measurement temperature was 25°C.

[Synthesis of cyanate prepolymer]

Production example A1

(Synthesis of cyanate prepolymer A)

In a 5L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 3,000 g of “AroCy B-10” (manufactured by Huntsman, brand name), a difunctional bisphenol A cyanate resin, 45.8 g of p-(α-cumyl)phenol (paracumylphenol) (manufactured by Mitsui Chemicals Fine Co., Ltd., brand name) and 1,303 g of toluene were added to prepare a reaction solution. The temperature of the reaction solution was started to rise, and the temperature of the reaction solution was stirred until the temperature reached 90°C. When 90°C was reached, 2.799 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., brand name, solid content concentration 8% by mass, mineral spirit solution cut) was added to the reaction solution. After that, the temperature was further raised to 110°C and stirred at 110°C for 180 minutes. Subsequently, toluene was added so that the solid content concentration of the reaction solution was 70% by mass, thereby obtaining cyanate prepolymer A (weight average molecular weight: about 3,200) dissolved in toluene.

[Production of resin film for interlayer insulating layer]

Reference example A1

(Production of resin film A1)

Each component and dimethylacetamide in the amounts shown in Table A1 were mixed so that the solid content concentration was 20% by mass, and stirred until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain resin varnish A1 for adhesion auxiliary layer.

Next, each component and toluene in the amounts shown in Table A2 were blended so that the solid content concentration was 72% by mass, and stirred until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain resin varnish A1 for interlayer insulating layer.

The resin varnish A1 for the adhesion auxiliary layer obtained above is applied on a PET film with a thickness of 38 ㎛ using a die coater and dried at 130 ° C. for 2 minutes to form an adhesive auxiliary layer with a support having a film thickness of 4 ㎛. got it Next, resin varnish A1 for interlayer insulating layer was applied on the formed adhesion auxiliary layer using a die coater and dried at 100°C for 1.5 minutes to form a resin composition layer for interlayer insulating layer (adhesion auxiliary layer and interlayer insulating layer) with a film thickness of 36㎛. The total thickness of the resin composition layers for layers was 40 μm), and resin film A1 was obtained.

Reference examples A2 to A14, A16 to A19

(Production of resin films A2 to A18)

With the compositions shown in Table A1 and Table A2, resin films A2 to A18 were obtained in the same procedure as Reference Example A1.

[Production of prepreg]

Reference example A15

(Production of prepreg A1)

With the composition shown in Table A1 and Table A2, resin varnish A15 for adhesion auxiliary layer and resin varnish A15 for interlayer insulating layer were obtained in the same procedure as in Reference Example A1.

Resin varnish A15 for adhesion auxiliary layer was applied on a 38 µm thick PET film using a die coater and dried at 140°C for 2 minutes to obtain an adhesion auxiliary layer with a support having a film thickness of 4 µm.

Next, resin varnish A15 for the interlayer insulating layer was impregnated into glass fibers (manufactured by Asahi Schwebel Co., Ltd., brand name: 2117 (E Glass)) and dried at 100°C for 8 minutes to form an interlayer layer containing glass fibers with a film thickness of 0.096 mm. A resin composition layer for an insulating layer (mass ratio of glass fibers was 40% by mass) was obtained. Next, the side of the obtained adhesion auxiliary layer with a support, which is not provided with a support, and the resin composition layer for an interlayer insulating layer containing glass fibers are placed facing each other, and a vacuum pressurized laminator "MVLP-500/600IIA" (Maiki Co., Ltd.) Prepreg A1 was obtained by vacuuming at 100°C for 30 seconds and pressurizing at 0.5 MPa for 30 seconds using Seisakusho (trade name).

At this time, in order to prevent the resin composition layer for the interlayer insulating layer containing glass fiber from being attached to unnecessary parts by the laminate, the adhesive auxiliary layer provided with a supporter, the resin composition layer for the interlayer insulating layer containing glass fiber, and the release PET The films were stacked and laminated in this order. As the release PET film, “Purex NR-1” (manufactured by Teijin DuPont Film Co., Ltd., brand name, thickness 38 μm) was used.

[Table A1]

The components in Table A1 are shown below.

[(a1) component]

·Cyanate prepolymer A: Cyanate prepolymer A synthesized in Preparation Example A1

[(b1) component]

NC-3000-H: Aralkyl novolac type epoxy resin having a biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100 mass%, epoxy equivalent weight: 289 g/eq)

[(c1) component]

Aerosil R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., brand name, solid content concentration 100 mass%, specific surface area: 100 m2/g)

YC100C: A silica filler (manufactured by Admatex Co., Ltd., brand name) treated with a phenylsilane coupling agent and the solid content concentration was adjusted to 50% by mass with MEK.

Sciqas: A 0.1 µm grade of silica filler (manufactured by Sakai Chemical Co., Ltd., brand name) treated with an epoxysilane coupling agent, and the solid content concentration was adjusted to 40% by mass with dimethylacetamide.

[(d1) component]

BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (manufactured by Nihon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, number average molecular weight: 26,000, weight average molecular weight: 110,000)

[Ingredients for comparison]

KS-9300: N-methylpyrrolidone solution of siloxane-containing polyamideimide resin (manufactured by Hitachi Kasei Co., Ltd., brand name, solid content concentration 33% by mass)

[(f1) component]

2PZ-CN: 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., brand name, solid concentration 100% by mass)

[(g1) component]

・KA1165: Cresol novolac resin (manufactured by DIC Corporation, brand name, hydroxyl equivalent weight: 119 g/eq)

[Table A2]

The components in Table A2 are shown below.

[(a2) component]

·Cyanate prepolymer A: Cyanate prepolymer A synthesized in Preparation Example 1

BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza, brand name, cyanate equivalent weight: 232 g/eq, MEK solution with solid content concentration of 75% by mass)

[(b2) component]

NC-7000-L: Novolak-type epoxy resin containing a naphthalene skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 231g/eq)

[(c2) component]

SO-C2: Globular silica treated with an aminosilane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, volume average particle size 0.5 μm, solid content concentration 100% by mass) )

[(f2) component]

2PZ-CN: 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., brand name, solid concentration 100% by mass)

・TPP: Triphenylphosphine (made by Liver Chemical Co., Ltd.)

・TPP-S: Triphenylphosphinetriphenylborane (manufactured by Hokko Chemical Industry Co., Ltd.)

2PZ-CNS-PW: 1-Cyanoethyl-2-undecylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

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

[(h2) component]

BYK-310: Resin having a siloxane skeleton (manufactured by Big Chemie Japan Co., Ltd., brand name, solid content concentration 25% by mass, diluted with xylene solvent)

[Table A3]

From Table A2, in particular, the interlayer insulating layer formed by the resin film and prepreg of Reference Examples A1 to A15 using the resin composition containing components (a1) to (d1) had no cracks or powder falling, The embeddedness of the wiring pattern was good. In addition, the laser processability and peel strength were excellent, and the surface roughness after desmear treatment was also small. In addition, the cured products of these resin films and prepregs had a small coefficient of thermal expansion and a low dielectric loss tangent.

[2-2] Reference example B

Next, the evaluation method and evaluation results of Reference Example B regarding the resin composition (2) of the present invention will be explained.

[Evaluation method in reference example B]

<Preservation rate of gelation time>

(1) Measurement of gelation time (gelation time 1) before storage

The protective film was taken and peeled from the resin film obtained in each example, and the resin composition containing the resin composition for an interlayer insulating layer and the resin composition for an adhesion auxiliary layer was peeled from the support. The resin composition was put into a gelation tester made of SUS plate (manufactured by Nissin Chemical Co., Ltd.) set at 180°C, stirred at a pace of 2 rotations per second using a large skewer, and gelled before storage. The time until gelation (gelation time 1) was measured.

(2) Measurement of gelation time (gelation time 2) after storage

The resin film obtained in each example was stored at 5°C, taken out after 30 days, returned to room temperature, and the resin composition was peeled from the support in the same procedure as above. For the obtained resin composition, the time until gelation after storage (gelation time 2) was measured in the same manner as for gelation time 1.

(3) Calculation of retention rate of gelation time

Using gelation time 1 and gelation time 2, the retention rate of gelation time was calculated using the following equation.

Retention rate of gelation time (%) = (gelation time 2/gelation time 1) × 100

The greater the storage ratio of the gelation time, the better the storage stability.

<maximum smear length>

For the resin films obtained in each example, the maximum smear length was measured according to the following procedures (1) to (6).

(1) Production of circuit board

A circuit pattern is created by etching on both sides of a glass cloth base epoxy resin double-sided copper clad laminate (manufactured by Hitachi Kasei Co., Ltd., product name: MCL-E-700G(R), copper foil thickness 12 ㎛, base material thickness 0.4 mm). was formed, and a roughening treatment was further performed using “Mech Etch Bond C (registered trademark) CZ8101” manufactured by Mack Co., Ltd. Additionally, rust prevention treatment was performed using “Mech Etch Bond (registered trademark) CL-8301” manufactured by Mack Co., Ltd. In this way, a circuit board was produced.

(2) Lamination method of interlayer insulating layer

The protective film was peeled from the resin film obtained in each example, and the resin composition layer for the interlayer insulating layer was placed on the circuit surface side of the circuit board, using a batch type vacuum pressure laminator "MVLP-500" (manufactured by Meiki Seisakusho Co., Ltd.) , product name) was used and laminated on both sides of the circuit board manufactured in (1). The laminate was depressurized for 30 seconds, the atmospheric pressure was lowered to 15 hPa or less, and then compressed at 100°C for 30 seconds at a pressure of 0.5 MPa.

(3) Curing of the interlayer insulation layer

After the sample obtained in (2) was cooled to room temperature, the support (PET film) was peeled off. After that, it was heated at 130°C for 20 minutes and then at 180°C for 40 minutes to cure the interlayer insulating layer resin composition layer to form an interlayer insulating layer.

(4) Method of forming via holes

Using a _CO2 laser processing machine "LC-2F21B" manufactured by Via Mechanics Co., Ltd., the interlayer insulating layer was processed in burst mode with a frequency of 2,000 kHz, a pulse width of 15 μs, and the number of shots was 4, and a via hole was created on the surface of the interlayer insulating layer. A via hole with a top diameter of 70 μm and a bottom diameter of the via hole at the bottom of the interlayer insulating layer of 60 μm was formed (taper ratio: via bottom diameter/via top diameter x 100 = about 86%).

(5) Desmear processing method

The sample with the via hole formed was immersed in a swelling liquid “Swelling Deep Securigant P” (manufactured by Atotech Japan Co., Ltd.) heated to 70°C for 10 minutes. Next, it was immersed in the cotton roughening liquid “Concentrate Compact CP” (manufactured by Atotech Japan Co., Ltd.) heated to 80°C for 10 minutes, and then the cotton roughening liquid “Reduction Securigant P500” (Atotech Japan Co., Ltd.) heated to 40°C. It was neutralized by immersion in Tek Japan Co., Ltd.) for 5 minutes.

(6) Evaluation method for smear removability

The area around the bottom of the via hole after the desmear treatment was observed using a scanning electron microscope (SEM) (made by Hitachi Seisakusho Co., Ltd., brand name: S-4700), and the maximum smear length from the wall of the bottom of the via hole was determined from the obtained image. Measured.

The smaller the maximum smear length, the better the smear (resin residue) removal ability.

<Number of reflow passes>

For the resin films obtained in each example, the number of reflow passages was measured according to the following procedures (1) to (3).

(1) Electroless plating treatment

Among the substrates after the desmear treatment shown in the evaluation method for smear removability, a portion on which no laser processing was performed was prepared as a sample.

The sample was first treated with an alkaline cleaner at 60°C, “Cleaner Securigant 902” (Atotech Japan Co., Ltd., brand name) for 5 minutes to degrease and clean. After washing, it was treated with "Predip Neogant B" (Atotech Japan Co., Ltd., brand name), a predip solution at 23°C, for 2 minutes. After that, treatment was performed for 5 minutes with “Activator Neogant 834” (trade name, manufactured by Atotech Japan Co., Ltd.), which is an activator liquid at 40°C, to cause the palladium catalyst to adhere. Next, it was treated with “Reducer Neogant WA” (Atotech Japan Co., Ltd., brand name), a reducing solution at 30°C, for 5 minutes. Next, chemical copper liquid [“Basic Printogant MSK-DK”, “Copper Solution Printogant MSK”, “Stabilizer Printogant MSK”] (all manufactured by Atotech Japan Co., Ltd., brand name) is added, and electroless plating is applied. This was carried out until the thickness reached about 0.5㎛. After electroless plating, a bake treatment was performed at 120°C for 15 minutes to relieve the stress remaining in the plating film and to remove remaining hydrogen gas.

(2) Electrolytic plating treatment

Next, electrolytic plating was performed on the electroless plated substrate at a rate of about 1.5 A/dm for 1 hour so that the plating thickness was about 30 μm. After electrolytic plating, heat treatment was performed at 190°C for 90 minutes. After cooling to room temperature, it was cut to a size of 40 mm x 40 mm, and 10 substrates for reflow heat resistance evaluation were produced.

(3) Reflow heat resistance evaluation test

The reflow device uses an air reflow system (model number: TAR30-366PN) manufactured by Tamura Seisakusho Co., Ltd., and the transfer speed is set to 0.61 m/min, and the inside of the reflow device is set to a maximum temperature of 260°C. did. The substrate for reflow heat resistance evaluation obtained above was passed through a reflow device up to 200 times, the number of passes until expansion occurred was measured, and the average value of 10 samples was taken as the number of reflow passes.

The greater the number of reflow passes, the better the reflow heat resistance.

[Synthesis of cyanate prepolymer]

Production example B1

In a 5 L separable flask, 1,436 parts by mass of toluene, 3,300 parts by mass of 2,2-bis(4-cyanatophenyl)propane (manufactured by Lonza, brand name: Primaset BADCy), and p-(α-cumyl)phenol. After adding and dissolving 50.40 parts by mass (manufactured by Tokyo Chemical Industry Co., Ltd.) and maintaining the liquid temperature at 100°C, zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., solid content 8% by mass, mineral) was added as a reaction accelerator. A solution of cyanate prepolymer B (weight average molecular weight: 3,441) with a solid content concentration of about 70% by mass was obtained by mixing 0.25 parts by mass of (spirit solution) and heating and reacting for about 3 hours.

[Manufacture of adhesion auxiliary layer with support]

Production example B2

Each component and dimethylacetamide in the amounts shown in Table B1 were mixed so that the solid content concentration was 20% by mass, and stirred until the resin component dissolved. After that, bead mill treatment was performed to obtain a resin varnish for an adhesion auxiliary layer.

The obtained resin varnish for adhesion auxiliary layer was applied to the treated surface of a 38 ㎛ thick PET film "NR-1" (Teijin DuPont Film Co., Ltd., brand name) using a die coater so that the thickness after application was 3 ㎛. After drying, an adhesion auxiliary layer with a support was obtained. The raw materials used are shown in Table B1.

[Table B1]

The components in Table B1 are shown below.

[(a1) component]

Cyanate prepolymer B: Cyanate prepolymer B synthesized in Production Example B1

[(b1) component]

NC-7000-L: Novolak-type epoxy resin containing a naphthalene skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 231g/eq)

[(d1) component]

BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (manufactured by Nihon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, number average molecular weight: 26,000, weight average molecular weight: 110,000)

[(f1) component]

2PZ-CN: 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., brand name, solid concentration 100% by mass)

[(h2) component]

BYK-310: Resin having a siloxane skeleton (manufactured by Big Chemie Japan Co., Ltd., brand name, solid content concentration 25% by mass, diluted with xylene solvent)

[Production of resin film for interlayer insulating layer]

Reference example B1

Each component in the amount shown in Table B2 was mixed and mixed for 5 hours until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain a resin varnish for an interlayer insulating layer.

The obtained resin varnish for interlayer insulating layer was applied to the surface of the support-equipped adhesion auxiliary layer on which the adhesion auxiliary layer was applied using a die coater so that the thickness after application was 37 ㎛ (40 ㎛ in total with the adhesion auxiliary layer) to form a resin film. got it

Reference examples B2 to B7

A resin film was obtained in the same manner as in Reference Example B1, except that the composition of the resin varnish for the interlayer insulating layer was changed to the composition shown in Table B2.

[Table B2]

The components in Table B2 are shown below.

[(a2) component]

Cyanate prepolymer B: Cyanate prepolymer B synthesized in Production Example B1

[(b2) component]

・N673: Cresol novolac type epoxy resin (manufactured by DIC Corporation, brand name, epoxy equivalent weight: 210 g/eq, solid content concentration 100% by mass)

・N730-A: Phenol novolac type epoxy resin (manufactured by DIC Corporation, brand name, epoxy equivalent weight: 176 g/eq, solid content concentration 100% by mass)

[(c2) component]

- "SO-C2" (manufactured by Admatex Co., Ltd., brand name), which is fused silica with an average particle diameter of 0.5 ㎛, is treated with the silane coupling agent shown below, so that the solid content concentration in MEK is 70% by mass. Dispersed silica slurry. Additionally, 20 parts by mass of each silane coupling agent was used per 1,000 parts by mass of “SO-C2”.

・Vinyl silane treated product: “KBM-1003” (manufactured by Shinetsu Chemical Co., Ltd., brand name, chemical name: vinyltrimethoxysilane)

・Epoxysilane treated product: “KBM-403” (manufactured by Shinetsu Chemical Co., Ltd., brand name, chemical name: 3-glycidoxypropyltrimethoxysilane)

· Aminosilane treated product: “KBM-573” (manufactured by Shin-Etsu Chemical Co., Ltd., brand name, chemical name: N-phenyl-3-aminopropyltrimethoxysilane)

[(e2) component]

YX7200B35: Phenoxy resin containing bisphenol TMC structure (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 35% by mass, MEK cut product)

[(f2) component]

2PZ-CN: 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., brand name, solid concentration 100% by mass)

[(g2) component]

・HPC-8000-65T: Active ester curing agent (manufactured by DIC Corporation, brand name, active ester equivalent weight: 223 g/eq, solid content concentration 65% by mass, toluene cut product)

[(h2) component]

BYK-310: Resin having a siloxane skeleton (manufactured by Big Chemie Japan Co., Ltd., brand name, solid content concentration 25% by mass, diluted with xylene solvent)

From Table B2, in particular, the resin compositions of Reference Examples B1 to B6 containing silica surface-treated with at least one silane coupling agent selected from the group consisting of an epoxysilane coupling agent and a vinylsilane coupling agent have excellent storage stability. , it can be seen that the obtained interlayer insulating layer is excellent in reflow heat resistance and smear removal properties.

[2-3] Reference example C

Next, the evaluation method and evaluation results of Reference Example C regarding the resin composition (2) of the present invention will be explained.

[Evaluation method in reference example C]

<Preservation rate of gelation time>

As described in the evaluation method in Reference Example B.

<Irregularities on the surface of the interlayer insulation layer>

In the method for evaluating the unevenness of the surface of the interlayer insulating layer in Reference Example A, the curing conditions of the laminated resin film were changed to 130°C for 20 minutes and then 180°C for 40 minutes. Measurements were performed in the same manner as in Reference Example A. did.

<maximum smear length>

As described in the evaluation method in Reference Example B.

<Surface roughness (Ra)>

The desmeared substrate used for the evaluation of the smear removability was used as a measurement sample, and the surface roughness after desmear was measured. Surface roughness was measured using a non-contact three-dimensional surface shape roughness meter "wykoNT9100" (Brooker AXS Co., Ltd., brand name) using an internal lens magnification of 1 and an external lens magnification of 50, and the surface roughness (Ra) was calculated. ) was calculated. The measurement was performed at n=10, and the average value was taken as the surface roughness (Ra) after desmearing.

<Thermal expansion coefficient>

The resin film obtained in each example was laminated to copper foil, then the PET film was peeled off and cured at 190°C for 2 hours in an explosion-proof dryer. The copper foil of the obtained sample was removed by etching, and what was cut into pieces with a length of 20 mm and a width of 4 mm was used as a sample for measuring the thermal expansion coefficient. Using “TMA-2940” (manufactured by TA Instruments, brand name) as a measuring device, the strain was removed by heating from room temperature to 260°C at a temperature increase rate of 10°C/min, then cooling to -20°C, and then heating to 10°C/min. The temperature was measured up to 300°C at a temperature increase rate of minutes. The average thermal expansion coefficient of 25 to 150°C was calculated, and this value was taken as the thermal expansion coefficient.

[Synthesis of cyanate prepolymer]

Production Example C1

(Synthesis of cyanate prepolymer C)

In a 5L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 3,000 g of “AroCy B-10” (manufactured by Huntsman, brand name), a difunctional bisphenol A cyanate resin, 45.8 g of p-(α-cumyl)phenol (paracumylphenol) (manufactured by Mitsui Chemicals Fine Co., Ltd., brand name) and 1,303 g of toluene were added to prepare a reaction solution. The temperature of the reaction solution was started to rise, and the reaction solution was stirred until the temperature reached 90°C. When 90°C was reached, 2.799 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., brand name, solid content concentration 8% by mass, mineral spirit solution cut) was added to the reaction solution. After that, the temperature was further raised to 110°C and stirred at 110°C for 180 minutes. Subsequently, toluene was further blended so that the solid content concentration of the reaction solution was 70% by mass, thereby obtaining cyanate prepolymer C (weight average molecular weight: 8, 230) dissolved in toluene.

[Production of adhesion auxiliary layer with support]

Production example C2

Each component and dimethylacetamide in the amounts shown in Table C1 were mixed so that the solid content concentration was 25% by mass, and stirred until the resin component was dissolved. Next, bead mill dispersion treatment was performed to obtain a resin varnish for an adhesion auxiliary layer.

The resin varnish for the adhesion auxiliary layer obtained above was applied using a die coater on a PET film with a thickness of 38 μm and dried at 130° C. for 2 minutes to obtain an adhesion auxiliary layer with a support having a film thickness of 4 μm. . The raw materials used are shown in Table C1.

[Table C1]

The components in Table C1 are shown below.

[(a1) component]

BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza, brand name, cyanate equivalent weight: 232 g/eq, MEK solution with solid content concentration of 75% by mass)

[(b1) component]

NC-3000-H: Aralkyl novolac type epoxy resin having a biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 289g/eq)

[(c1) component]

Aerosil R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., brand name, solid content concentration 100 mass%, specific surface area: 100 m2/g)

[(d1) component]

BPAM-155: A rubber-modified polyamide resin having an amino group at the terminal (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, number average molecular weight: 26,000, weight average molecular weight: 110,000) was previously dissolved in dimethylacetamide. Dissolved so that the solid content concentration is 10% by mass.

[(e1) component]

YX7200B35: Phenoxy resin containing bisphenol TMC structure (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 35% by mass, MEK cut product)

[(f1) component]

Curing accelerator 1: Addition reaction product of tris(p-methylphenyl)phosphine and 1,4-benzoquinone synthesized with reference to Japanese Patent Application Laid-Open No. 2011-179008 (solid concentration 100% by mass)

[Production of resin film for interlayer insulating layer]

Reference example C1

Each component and toluene in the amounts shown in Table C2 were mixed so that the solid content concentration was 70% by mass, and stirred until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain a resin varnish for an interlayer insulating layer.

Next, the resin varnish for the interlayer insulating layer was applied onto the adhesion auxiliary layer of the adhesion auxiliary layer with a support obtained in Production Example C2 using a die coater, and dried at 100° C. for 1.5 minutes to obtain a resin composition for the interlayer insulating layer with a film thickness of 36 μm. A layer (total thickness of the adhesion auxiliary layer and the resin composition layer for interlayer insulating layer is 40 μm) was formed to obtain a resin film.

Reference examples C2 to C16

A resin film was obtained in the same manner as in Reference Example C1, except that the composition of the resin varnish for the interlayer insulating layer was changed to the composition shown in Table C2.

[Table C2]

The components in Table C2 are shown below.

[(a2) component]

Cyanate prepolymer C: Cyanate prepolymer C synthesized in Production Example C1 (solid content concentration 70% by mass)

BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza Corporation, brand name, cyanate equivalent weight: 232 g/eq, MEK solution with a solid content concentration of 75% by mass)

[(b2) component]

NC-7000-L: Novolak-type epoxy resin containing a naphthalene skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 231g/eq)

・N673: Cresol novolac type epoxy resin (manufactured by DIC Corporation, brand name, solid content concentration 100% by mass, epoxy equivalent: 210g/eq)

・Ep828: Liquid epoxy resin of bisphenol A type (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 100% by mass, epoxy equivalent weight: 185g/eq)

[(c2) component]

Vinyl silane treated product: spherical silica “SO-C2” (manufactured by Admatex Co., Ltd., brand name, average particle size: 0.5 ㎛) surface-treated with a vinyl silane coupling agent (vinyltrimethoxysilane) is mixed with a solvent ( Silica slurry dispersed in MEK) so that the solid content concentration is 70% by mass.

·Epoxysilane treated product: “SO-C2”, a spherical silica surface treated with an epoxysilane coupling agent (3-glycidoxypropyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, average particle size: 0.5) ㎛) silica slurry dispersed in a solvent (MEK) so that the solid concentration is 70% by mass.

Aminosilane-treated product: “SO-C2”, a spherical silica treated with an aminosilane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, average particle size: 0.5) ㎛) silica slurry dispersed in a solvent (MEK) so that the solid concentration is 70% by mass.

[(e2) component]

YX7200B35: Phenoxy resin containing bisphenol TMC structure (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 35% by mass, MEK cut product)

1256: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 100% by mass)

YX6954: Phenoxy resin containing bisphenol acetophenone skeleton (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 30% by mass)

[(f2) component]

Curing accelerator 1: Addition reaction product of tris(p-methylphenyl)phosphine and 1,4-benzoquinone synthesized with reference to Japanese Patent Application Laid-Open No. 2011-179008 (solid concentration 100% by mass)

[(g2) component]

・HPC-8000-65T: Active ester curing agent (manufactured by DIC Corporation, brand name, active ester equivalent weight: 223 g/eq, solid content concentration 65% by mass, toluene cut product)

Dicyandiamide: A solution (solids concentration of 3% by mass) obtained by dissolving (manufactured by Nippon Carbide Kogyo Co., Ltd., solid content concentration 100% by mass) in an organic solvent (propylene glycol monomethyl ether (PGM)).

[(h2) component]

BYK-310: Resin having a siloxane skeleton (manufactured by Big Chemie Japan Co., Ltd., brand name, solid content concentration 25% by mass, diluted with xylene solvent)

[(i2) component]

・p-cumylphenol: (manufactured by Tokyo Kasei Kogyo Co., Ltd., solid content concentration 100% by mass)

From Table C2, in particular, the interlayer insulation formed by the resin films of Reference Examples C1 to C11 using a resin composition containing component (a2), component (b2), component (c2) and a phenoxy resin containing an alicyclic structure. The layer had good storage stability, and the unevenness of the surface of the interlayer insulating layer was small, so the embedding property of the wiring pattern was good. In addition, in the desmear after laser processing, good smear removal properties were exhibited and the surface roughness was also small. Additionally, the cured products of these resin films had a small coefficient of thermal expansion.

[2-4] Reference example D

Next, the evaluation method and evaluation results of Reference Example D regarding the resin composition (2) of the present invention will be explained.

[Evaluation method in reference example D]

<Appearance after curing after attachment to support>

Appearance evaluation after attachment and curing of the support (PET) was performed in the following procedure.

First, the resin film obtained in each example was cut to 200 mm on each side, the protective film was peeled off, and the resin composition layer for the interlayer insulating layer was placed so as to face the circuit surface of the printed wiring board, and then laminated.

The printed wiring board is a copper-clad laminate "MCL-E-679FG" (manufactured by Hitachi Kasei Co., Ltd., brand name) with a 35 ㎛ thick copper layer, and a circuit is processed with an arbitrary residual copper content of 0 to 95% by the subtractive method. This was used.

In addition, the laminating device was performed using a vacuum pressurized laminator "MVLP-500/600IIA" (made by Meiki Seisakusho Co., Ltd., brand name), and after vacuuming at 110°C for 30 seconds, pressure was applied at 0.5 MPa for 30 seconds. . After that, hot pressing was performed at 110°C for 60 seconds and 0.5 MPa.

Next, after cooling to room temperature, curing was performed in an explosion-proof dryer at 130°C for 20 minutes, followed by 180°C for 40 minutes, with the PET film as a support attached, to produce an appearance evaluation board after curing with the support attached.

Appearance evaluation was performed visually, and the case where no voids or delamination was visible between the interlayer insulating layer and the printed wiring board on the front and back of the evaluation board was evaluated as “A”, and the case where there was one or more voids or delamination was evaluated as “B”.

<maximum smear length>

As described in the evaluation method in Reference Example B.

<Dielectric loss tangent>

The resin films obtained in each example were heat-cured by heating at 190°C for 90 minutes, and then the support was peeled off to obtain a sheet-like cured product. The cured product was cut into pieces with a length of 80 mm and a width of 2 mm, which were used as evaluation samples. For this evaluation sample, the dielectric loss tangent was measured by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C.

<Number of reflow passes>

A substrate after the desmear treatment obtained was produced in the same procedures as (1) to (3) and (5) in the method for measuring the maximum smear length in Reference Example B ((4) without forming via holes).

The substrate obtained above was immersed in "Cleaner Securigant 902" (manufactured by Atotech Japan Co., Ltd.) as a cleaner at 60°C for 5 minutes, and then as a pre-dip with "Pre-dip Neogant B" (manufactured by Atotech Japan). Co., Ltd. product) at 25°C for 2 minutes, “Activator Neogant 834” as a cedar at 40°C for 5 minutes, “Reducer Neogant WA” as a reducer at 30°C for 5 minutes, and electroless plating with “MSK-DK”. An immersion treatment was performed at 30°C for 30 minutes to form an electroless plating layer of 200 to 250 nm. Additionally, in a copper sulfate plating bath, an electroplating layer with a plating thickness of 25 to 30 μm was formed at a current density of 2 A/dm 2 .

Next, the obtained substrate after electroplating was cut into 40 mm on each side, and 10 substrates for heat resistance evaluation were produced.

As a reflow device, an air reflow system (model number: TAR-30-366PN) manufactured by Tamura Seisakusho Co., Ltd. was used, and the inside of the reflow device was set to a maximum temperature of 260°C. The heat resistance evaluation board obtained above was passed through a reflow device up to 200 times, the number of passes until expansion occurred was measured, and the average value of 10 samples was taken as the average number of reflow passes.

[Synthesis of cyanate prepolymer]

Production Example D1

(Synthesis of cyanate prepolymer D)

In a 5L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 3,000 g of “AroCy B-10” (manufactured by Huntsman, brand name), a difunctional bisphenol A cyanate resin, 45.8 g of p-(α-cumyl)phenol (paracumylphenol) (manufactured by Mitsui Chemicals Fine Co., Ltd., brand name) and 1,303 g of toluene were added to prepare a reaction solution. The temperature of the reaction solution was started to rise, and the temperature of the reaction solution was stirred until the temperature reached 90°C. When 90°C was reached, 2.799 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., brand name, solid content concentration 8% by mass, mineral spirit solution cut) was added to the reaction solution. After that, the temperature was further raised to 110°C and stirred at 110°C for 180 minutes. Subsequently, toluene was added so that the solid content concentration of the reaction solution was 70% by mass, thereby obtaining cyanate prepolymer D (weight average molecular weight: 8,230) dissolved in toluene.

[Method for manufacturing adhesion auxiliary layer with support]

Production example D2

Each component and dimethylacetamide in the amounts shown in Table D1 were mixed so that the solid content concentration was 25% by mass, and stirred until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain a resin varnish for an adhesion auxiliary layer.

The resin varnish for the adhesion auxiliary layer obtained above was applied using a die coater on the release-treated PET film with a thickness of 38 ㎛, and dried at 130 ° C. for 2 minutes, so that the adhesion auxiliary layer was provided with a support of 4 ㎛ in thickness. Got a layer. The raw materials used are shown in Table D1.

[Table D1]

The components in Table D1 are shown below.

[(a1) component]

BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza, brand name, cyanate equivalent weight: 232 g/eq, MEK solution with solid content concentration of 75% by mass)

[(b1) component]

NC-3000-H: Aralkyl novolac type epoxy resin having a biphenyl skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 289g/eq)

[(c1) component]

Aerosil R972: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., brand name, solid content concentration 100 mass%, specific surface area: 100 m2/g)

[(d1) component]

BPAM-155: Rubber-modified polyamide resin having an amino group at the terminal (Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, number average molecular weight: 26,000, weight average molecular weight: 110,000). In addition, BPAM-155 was added in a state in which it was previously dissolved in dimethylacetamide so that the solid content concentration was 10% by mass.

[(e1) component]

YX1256B40: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 40% by mass, MEK cut product)

[(f1) component]

Curing accelerator 1: Addition reaction product of tributylphosphine and 1,4-benzoquinone synthesized with reference to Japanese Patent Application Laid-Open No. 2011-179008 (solid concentration 100% by mass)

[Production of resin film for interlayer insulating layer]

Reference example D1

Each component and toluene in the amounts shown in Table D2 were mixed so that the solid content concentration was 70% by mass, and stirred until the resin component dissolved. Next, bead mill dispersion treatment was performed to obtain a resin varnish for an interlayer insulating layer.

Next, the resin varnish for the interlayer insulating layer was applied onto the adhesion auxiliary layer of the adhesion auxiliary layer with a support obtained in Production Example D2 using a die coater, and dried at 100° C. for 1.5 minutes to obtain a resin composition for the interlayer insulating layer with a film thickness of 36 μm. A layer (total thickness of the adhesion auxiliary layer and the resin composition layer for interlayer insulating layer is 40 μm) was formed to obtain a resin film.

Reference examples D2 to D14

A resin film was obtained in the same manner as in Reference Example D1, except that the composition of the resin varnish for the interlayer insulating layer was changed to the composition shown in Table D2.

[Table D2]

The components in Table D2 are shown below.

[(a2) component]

BA230S75: Prepolymer of bisphenol A dicyanate (manufactured by Lonza, brand name, cyanate equivalent weight: 232 g/eq, MEK solution with solid content concentration of 75% by mass)

Cyanate prepolymer D: Cyanate prepolymer D synthesized in Production Example 1 (solid content concentration 70% by mass)

[(b2) component]

・N673: Cresol novolac type epoxy resin (manufactured by DIC Corporation, brand name, epoxy equivalent weight: 210 g/eq, solid content concentration 100% by mass)

NC-7000-L: Novolak-type epoxy resin containing a naphthalene skeleton (manufactured by Nippon Kayaku Co., Ltd., brand name, solid content concentration 100% by mass, epoxy equivalent weight: 231g/eq)

840S: Bisphenol A type liquid epoxy resin (manufactured by DIC Corporation, brand name, solid content concentration 100 mass%, epoxy equivalent weight: 185 g/eq)

[(c2) component]

Vinyl silane treated product: “SO-C2”, a spherical silica treated with a vinyl silane coupling agent (vinyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, volume average particle size 0.5 ㎛, solid content concentration 100 mass%) )

·Epoxysilane treated product: “SO-C2”, a spherical silica treated with an epoxysilane coupling agent (3-glycidoxypropyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, volume average particle size 0.5㎛, Solid content concentration 100% by mass)

Aminosilane-treated product: “SO-C2”, a spherical silica treated with an aminosilane coupling agent (N-phenyl-3-aminopropyltrimethoxysilane) (manufactured by Admatex Co., Ltd., brand name, volume average particle size 0.5) ㎛, solid content concentration 100% by mass)

[(e2) component]

YX1256B40: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, brand name, solid content concentration 40% by mass, MEK cut product)

[(f2) component]

Curing accelerator 1: Addition reaction product of tributylphosphine and 1,4-benzoquinone represented by the following formula (f-7) synthesized with reference to Japanese Patent Application Laid-Open No. 2011-179008 (solid concentration 100% by mass) )

Curing accelerator 2: Addition reaction product of tris(p-methylphenyl)phosphine and 1,4-benzoquinone represented by the following formula (f-8) synthesized with reference to Japanese Patent Application Laid-Open No. 2011-179008 (solid content) Concentration 100% by mass)

2PZ-CN: 1-Cyanoethyl-2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., solid concentration 100% by mass)

DMAP: N,N-dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration 100% by mass)

[(g2) component]

・HPC-8000-65T: Active ester curing agent (manufactured by DIC Corporation, brand name, active ester equivalent weight: 223 g/eq, solid content concentration 65% by mass, toluene cut product)

·Dicyandiamide: (manufactured by Nippon Carbide Kogyo Co., Ltd., solid content concentration 100% by mass)

[(h2) component]

BYK330: Resin having a siloxane skeleton (manufactured by Big Chemie Japan Co., Ltd., brand name, solid content concentration 25% by mass, xylene cut product)

From Table D2, in particular, the interlayer insulating layer formed by the resin film of Reference Examples D1 to D10 using a resin composition containing a phosphorus-based curing accelerator has an excellent appearance and good smear removability even when cured with a support (PET) attached. indicated. Additionally, it was found that the dielectric loss tangent was small and the heat resistance was sufficient.

Claims (12)

Contains at least one selected from the group consisting of (a2) cyanate resin, (b2) epoxy resin, and (c2) inorganic filler, (e2) phenoxy resin, (f2) curing accelerator, and (g2) epoxy resin curing agent. Resin composition (2). The resin composition (2) according to claim 1, wherein (c2) the inorganic filler is surface treated with at least one surface treatment agent selected from the group consisting of a vinyl silane coupling agent and an epoxy silane coupling agent. The resin composition (2) according to claim 2, wherein the inorganic filler (c2) contains silica surface-treated with an epoxysilane coupling agent and silica surface-treated with a vinylsilane coupling agent. The resin composition (2) according to claim 1, containing (e2) a phenoxy resin. The resin composition (2) according to claim 4, wherein the phenoxy resin (e2) is a phenoxy resin containing an alicyclic structure. The resin composition (2) according to claim 1, which contains (f2) a curing accelerator. The resin composition (2) according to claim 6, wherein (f2) the curing accelerator is a phosphorus-based curing accelerator. The resin composition (2) according to claim 1, containing (g2) an epoxy resin curing agent. The resin composition (2) according to claim 8, which (g2) contains an active ester curing agent as the epoxy resin curing agent. It is a resin film for an interlayer insulating layer having a support, an adhesion auxiliary layer, and a resin composition layer for an interlayer insulating layer in this order,
A resin film for an interlayer insulating layer, wherein the resin composition layer for an interlayer insulating layer is a layer containing the resin composition (2) according to any one of claims 1 to 9. A multilayer printed wiring board comprising a cured product of the resin composition (2) according to any one of claims 1 to 9. A semiconductor package using the multilayer printed wiring board according to claim 11.