JP6953709B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Further, the present invention relates to a sheet-like laminated material, an adhesive film, a printed wiring board, and a semiconductor device containing the resin composition.

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 describes a resin composition containing (A) an epoxy resin having an ester skeleton, (B) an active ester-type curing agent, and (C) an inorganic filler, and is a non-volatile component in the resin composition. When 100% by mass, (C) the content of the inorganic filler is 50% by mass or more, and when (C) the inorganic filler is 100 parts by mass, (A) the epoxy resin having an ester skeleton is 1. A resin composition of up to 20 parts by mass is disclosed.

Japanese Unexamined Patent Publication No. 2014-177530

In recent years, as circuit wiring is required to have a higher density, the number of laminated layers due to the build-up of printed wiring boards tends to increase. However, as the number of layers increases, the heat between the insulating layer and the conductor layer tends to increase. Cracks and circuit distortion may occur due to the difference in expansion coefficient. Patent Document 1 attempts to solve cracks and circuit distortion by increasing the content of the inorganic filler.

However, if the content of the inorganic filler is increased, the minimum melt viscosity of the resin composition becomes too high. Therefore, instead of increasing the content of the inorganic filler, it is conceivable to use a thermosetting resin having a low crosslink density (epoxy resin, etc.), but the thermosetting resin having a low crosslink density heat-cures the resin composition. Easy to volatilize in the process. Under these circumstances, the present inventors have found that it is difficult to obtain a resin composition having a low minimum melt viscosity and an excellent balance of physical properties by the conventional technique.

An object of the present invention is a resin composition that provides an insulating layer having a low minimum melt viscosity, low roughness, and high peel strength; a sheet-like laminated material containing the resin composition; and containing the resin composition. Adhesive film; An object of the present invention is to provide a printed wiring board provided with an insulating layer formed by using the resin composition, and a semiconductor device.

As a result of diligent studies to solve the above problems, the present inventors have made a minimum of the resin composition by incorporating (A) a monofunctional epoxy resin having a biphenyl structure and (B) a curing agent in the resin composition. They have found that they provide an insulating layer having a low melt viscosity, a low dielectric loss tangent, a low roughness, and a high peel strength, and have completed the present invention.

（式中、Ｒは、単結合又は２価の連結基を表す。）
［３］ 一般式（１）中のＲが、酸素原子、硫黄原子、−ＮＨ−、−Ｃ（＝Ｏ）−、−ＳＯ−、置換基を有していてもよいアルキレン基、置換基を有していてもよいアリーレン基、又はこれらの２つ以上の組み合わせからなる基を表す、［２］に記載の樹脂組成物。
［４］ 一般式（１）中のＲが、酸素原子、及び置換基を有していてもよいアルキレン基の組み合わせからなる基を表す、［２］又は［３］に記載の樹脂組成物。
［５］ （Ａ）成分が、下記化合物である、［１］〜［４］のいずれかに記載の樹脂組成物。

［６］ （Ａ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、１〜２０質量％である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ （Ｂ）成分が、フェノール系硬化剤、シアネートエステル系硬化剤、及び活性エステル系硬化剤から選択される、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ さらに、（Ｃ）無機充填材を含む、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ （Ｃ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、５０質量％以上である、［８］に記載の樹脂組成物。
［１０］ プリント配線板の絶縁層形成用である、［１］〜［９］のいずれかに記載の樹脂組成物。
［１１］ ［１］〜［１０］のいずれかに記載の樹脂組成物を含む、シート状積層材料。
［１２］ 支持体と、該支持体上に設けられた、［１］〜［１０］のいずれかに記載の樹脂組成物で形成された樹脂組成物層とを含む、接着フィルム。
［１３］ 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
該絶縁層は、［１］〜［１０］のいずれかに記載の樹脂組成物の硬化物である、プリント配線板。
［１４］ ［１３］に記載のプリント配線板を備える、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) a monofunctional epoxy resin having a biphenyl structure and (B) a curing agent.
[2] The resin composition according to [1], wherein the component (A) is a compound represented by the following general formula (1).

(In the formula, R represents a single bond or a divalent linking group.)
[3] R in the general formula (1) is an oxygen atom, a sulfur atom, -NH-, -C (= O)-, -SO-, an alkylene group which may have a substituent, or a substituent. The resin composition according to [2], which represents an arylene group which may be possessed or a group consisting of a combination of two or more thereof.
[4] The resin composition according to [2] or [3], wherein R in the general formula (1) represents a group consisting of a combination of an oxygen atom and an alkylene group which may have a substituent.
[5] The resin composition according to any one of [1] to [4], wherein the component (A) is the following compound.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (A) is 1 to 20% by mass when the non-volatile component in the resin composition is 100% by mass. thing.
[7] The resin composition according to any one of [1] to [6], wherein the component (B) is selected from a phenol-based curing agent, a cyanate ester-based curing agent, and an active ester-based curing agent.
[8] The resin composition according to any one of [1] to [7], further comprising (C) an inorganic filler.
[9] The resin composition according to [8], wherein the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[10] The resin composition according to any one of [1] to [9], which is used for forming an insulating layer of a printed wiring board.
[11] A sheet-like laminated material containing the resin composition according to any one of [1] to [10].
[12] An adhesive film comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [10].
[13] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [10].
[14] A semiconductor device including the printed wiring board according to [13].

According to the present invention, a resin composition that provides an insulating layer having a low minimum melt viscosity, low dielectric loss tangent, low roughness, and high peel strength; a sheet-like laminated material containing the resin composition; the resin. An adhesive film containing a composition; a printed wiring board provided with an insulating layer formed by using the resin composition, and a semiconductor device can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, the sheet-like laminated material, the adhesive film, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) a monofunctional epoxy resin having a biphenyl structure and (B) a curing agent. Thereby, a resin composition having a low minimum melt viscosity can be obtained. Then, this resin composition can provide an insulating layer having a low dielectric loss tangent, a low roughness, and a high peel strength. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Monofunctional epoxy resin having a biphenyl structure>
The resin composition contains (A) a monofunctional epoxy resin having a biphenyl structure. Here, the monofunctional epoxy resin represents an epoxy resin having one epoxy group in the molecule. The component (A) acts as a diluent in the resin composition. It is considered that this lowers the minimum melt viscosity. Further, since the component (A) is hard to volatilize, the volatilization of the component (A) is suppressed when the resin composition is thermally cured. As a result, the decrease in the cross-linking density of the component (A) cured by the component (B) is suppressed. It is considered that this makes it possible to provide a resin composition that provides an insulating layer having low roughness and high peel strength. Further, since the polarity of the polymer obtained by cross-linking the component (A) is small, the dielectric loss tangent of the insulating layer containing the polymer can be lowered.

The component (A) is not particularly limited as long as it is a monofunctional epoxy resin having a biphenyl structure (biphenyl group), and the component (A) is preferably a liquid monofunctional epoxy resin having a biphenyl structure. Further, the component (A) may have a plurality of biphenyl structures in the molecule, and a substituent such as an alkyl group or an alkoxy group may be bonded to the biphenyl structure. The number of carbon atoms of these substituents is usually 1 to 6 (preferably 1 to 3).

The biphenyl structure and the epoxy group may be directly bonded, and may have an oxygen atom, a sulfur atom, -NH-, -C (= O)-, -SO-, and an alkylene group which may have a substituent. It may be bonded via a divalent linking group consisting of an arylene group which may have a substituent, a group consisting of two or more combinations thereof, or the like, and is bonded via a divalent linking group. It is preferable to do so.

（式中、Ｒは、単結合又は２価の連結基を表す。） The component (A) is preferably represented by the following general formula (1).

(In the formula, R represents a single bond or a divalent linking group.)

R represents a single bond or a divalent linking group, and a divalent linking group is preferable. The divalent linking group includes, for example, an oxygen atom, a sulfur atom, -NH-, -C (= O)-, -SO-, an alkylene group which may have a substituent, and a substituent. Examples thereof include an arylene group which may be used, or a group consisting of a combination of two or more of these.

As the alkylene group which may have a substituent, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms is preferable. An alkylene group having 1 to 3 carbon atoms is more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1,1-dimethylethylene group and the like, and a methylene group, an ethylene group and 1,1 -The dimethylethylene group is preferable, and the methylene group is more preferable.

The alkylene group may have a substituent. The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-. Examples thereof include a _{10 aryl group, -NH 2} , -CN, -C (O) O-C _1-6 alkyl group, -COOH, -C (O) H, -NO _{2 and the} like.

Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, _{the expression "C 1-6} alkyl group" refers to an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the secondary substituent may be the same as the above-mentioned substituent.

As the arylene group which may have a substituent, an arylene group having 6 to 14 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group and the like. The substituent which the arylene group may have is the same as the substituent which the alkylene group may have.

The group consisting of a combination of two or more of these has a group (having an oxygen atom and a substituent) in which one or more oxygen atoms and an alkylene group which may have one or more substituents are bonded. A group consisting of a combination of alkylene groups which may be present), a group in which one or more sulfur atoms and an alkylene group which may have one or more substituents are bonded, and one or more oxygen atoms and one. Examples thereof include a group in which an arylene group which may have the above substituents is bonded and a group in which one or more sulfur atoms and an arylene group which may have one or more substituents are bonded. ..

Among these, R may have an oxygen atom, a sulfur atom, -NH-, -C (= O)-, -SO-, an arylene group which may have a substituent, and a substituent. Of the good alkylene groups, a group consisting of a combination of two or more is preferable, and a group consisting of a combination of an oxygen atom and an alkylene group which may have a substituent is more preferable.

The position of R bonded to the benzene ring contained in the biphenyl structure is arbitrary, and may be any of the ortho position, the meta position, and the para position. Above all, the ortho position is preferable in order to obtain a remarkable effect.

Hereinafter, specific examples (exemplary compounds) of the component (A) will be shown, but the component (A) is not limited thereto.

As the component (A), a commercially available product may be used, for example, "SY-OPG" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. (the above-mentioned example compound) and "EX-142" (the above-mentioned example compound) manufactured by Nagase ChemteX Corporation. And so on.

The viscosity of the component (A) at 25 ° C. is preferably 1000 mPa · s or less, more preferably 500 mPa · s or less, still more preferably 300 mPa · s or less, from the viewpoint of lowering the minimum melt viscosity of the resin composition. As the lower limit, from the viewpoint of making the surface of the insulating layer low in roughness, 50 mPa · s or more is preferable, 100 mPa · s or more is more preferable, and 150 mPa · s or more is further preferable. The viscosity of the component (A) shall be measured at 25 ° C. and 20 rpm using, for example, an E-type viscometer (using a “RE-25U” manufactured by Toki Sangyo Co., Ltd., a cone rotor of 1 ° 34 ′ × R24). Can be done.

The epoxy equivalent of the component (A) is preferably 50 to 3000, more preferably 50 to 1000, still more preferably 80 to 800, and even more preferably 110 to 500. Within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The content of the component (A) in the resin composition is such that the minimum melt viscosity of the resin composition is lowered, the dielectric loss tangent is low, the roughness is low, and an insulating layer having high peel strength is obtained. When the non-volatile component in the product is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit of the content of the component (A) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. ..

<(B) Hardener>
The resin composition contains (B) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the component (A) (when the resin composition contains the epoxy resin (D) described later, the components (A) and (D)), for example. Examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. The curing agent may be used alone or in combination of two or more. The component (B) is preferably one or more selected from a phenol-based curing agent, a cyanate ester-based curing agent, and an active ester-based curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwakasei Workers, and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395", manufactured by Nippon Steel & Sumitomo Metal Corporation, Examples thereof include "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

The active ester-based curing agent is not particularly limited, but generally contains one molecule of an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds having two or more of them are preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of the active ester-based curing agent include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" (manufactured by DIC) as an active ester compound containing an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac. Examples of the active ester-based curing agent which is a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which a part or all of bisphenol A disianate is triazined to form a trimer) and the like.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The amount ratio of the component (A) to the component (B) is a ratio of [total number of epoxy groups of the component (A)]: [total number of reactive groups of the component (B)] from 1: 0.01 to The range of 1: 3 is preferable, 1: 0.015 to 1: 2 is more preferable, and 1: 0.02 to 1: 2 is even more preferable. Here, the reactive group of the component (B) is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of curing agent. The total number of epoxy groups in the component (A) is the sum of the values obtained by dividing the solid content mass of each component (A) by the epoxy equivalent for all the components (A), and the total number of the epoxy groups in the component (B). The total number of reactive groups is a value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent and the total value for all the curing agents. By setting the amount ratio of the component (A) to the component (B) within such a range, the heat resistance of the cured product of the resin composition layer is further improved.

The content of the component (B) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably. Is 10% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. By setting the content of the curing agent to 1% by mass or more, the decrease in the crosslink density of the component (A) can be suppressed and the plating peel strength can be improved. Insulation layer can be formed.

<(C) Inorganic filler>
The resin composition may contain (C) an inorganic filler in addition to the components (A) to (B) from the viewpoint of reducing the dielectric loss tangent and the minimum melt viscosity of the insulating layer.

The material of the inorganic filler is an inorganic material, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably 0.3 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex, and "UFP-30" manufactured by Denki Kagaku Kogyo. , Tokuyama Corporation "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex Co., Ltd. "SO-C2", "SO-C1" and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler contains a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, and an alkoxysilane. It is preferably treated with one or more surface treatment agents such as a compound, an organosilazane compound, and a titanate-based coupling agent, and more preferably treated with a fluorine-containing silane coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) and the like.

The degree of surface treatment with the surface treatment agent is such that the surface treatment is performed with 0.2 parts by mass to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the inorganic filler from the viewpoint of improving the dispersibility of the inorganic filler. The surface treatment is preferably 0.2 parts by mass to 3 parts by mass, and the surface treatment is preferably 0.3 parts by mass to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

When the resin composition contains an inorganic filler, the content of the inorganic filler is determined when the non-volatile component in the resin composition is 100% by mass from the viewpoint of reducing the dielectric loss tangent and the minimum melt viscosity of the insulating layer. It is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, or 75% by mass from the viewpoint of the mechanical strength of the insulating layer. % Or less.

<(D) Epoxy resin (excluding monofunctional epoxy resin having a biphenyl structure)>
The resin composition may contain (D) epoxy resin in addition to the components (A) to (B) from the viewpoint of obtaining an insulating layer exhibiting insulation reliability. However, the (D) epoxy resin referred to here does not include the (A) monofunctional epoxy resin having a biphenyl structure.

Examples of the epoxy resin include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy resin; bisphenol S type epoxy resin; bixyleneol. Type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type Epoxy resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; cresol novolac type epoxy resin; biphenyl type epoxy resin (excluding biphenyl type monofunctional epoxy resin); linear aliphatic epoxy resin; epoxy resin having a butadiene structure; Oil ring type epoxy resin; heterocyclic type epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin and the like can be mentioned. The epoxy resin (D) may be used alone or in combination of two or more.

The epoxy resin (D) preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin (D) is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. (D) The epoxy resin has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”), and / or three or more in one molecule. It is preferable that the epoxy resin has the above-mentioned epoxy group and is solid at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). As the (D) epoxy resin, a liquid epoxy resin and a solid epoxy resin may be used in combination.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, and "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumitomo Metal Corporation. (Mixed product of type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation, "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation. , "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Co., Ltd., "ZX1658", "ZX1658GS" manufactured by Nippon Steel Chemical Co., Ltd. ( Liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd., etc. Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin (biphenyl type monofunctional epoxy resin). (Excluding), naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, bixilenol type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and bi Xylenol type epoxy resin is more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311" , "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayakusha ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd. "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin), "YX8800" (Anthracen type epoxy resin), Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "jER1010", ( Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin) and the like.

(D) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is 1: 0.1 to 1:15 in terms of mass ratio. Is preferable, the range of 1: 0.1 to 1:10 is more preferable, and the range of 1: 0.3 to 1: 3 is even more preferable.

The epoxy equivalent of the epoxy resin (D) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided.

The weight average molecular weight of the epoxy resin (D) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500.

When the resin composition contains (D) epoxy resin, the content of (D) epoxy resin is a non-volatile component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good tensile strength and insulation reliability. When it is 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit of the content of the epoxy resin (D) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less. be.

The amount ratio of the component (D) to the component (B) is a ratio of [total number of epoxy groups of the component (D)]: [total number of reactive groups of the component (B)] from 1: 0.01 to The range of 1: 3 is preferable, 1: 0.015 to 1: 2 is more preferable, and 1: 0.02 to 1: 2 is even more preferable. The total number of reactive groups of the component (B), the total number of epoxy groups of the component (D), and the total number of reactive groups of the component (B) are as described above. By setting the amount ratio of the component (D) to the component (B) within such a range, the heat resistance of the cured product of the resin composition layer is further improved.

<(E) Thermoplastic resin>
In one embodiment, the resin composition may contain (E) a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples thereof include ether ketone resin and polyester resin, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 40,000 or more. The upper limit is not particularly limited, but is preferably 70,000 or less, more preferably 60,000 or less. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K- manufactured by Showa Denko Corporation as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. (Skeletal-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation. , "YL6794", "YL7213", "YL7290", "YL7482" and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electric butyral 4000-2", "electric butyral 5000-A", "electric butyral 6000-C", "electric butyral 6000-EP", and Sekisui manufactured by Denki Kagaku Kogyo Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Shin Nihon Rika Co., Ltd. Specific examples of the polyimide resin include a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include an oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company, Inc., which has a vinyl group.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the wiring circuit can be miniaturized.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. The mass% is more preferable, and 1% by mass to 5% by mass is further preferable.

<(F) Organic filler>
In one embodiment, the resin composition may contain (F) an organic filler. By containing the component (F), the tensile breaking strength of the cured product of the resin composition can be improved. As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

As the rubber particles, commercially available products may be used, and examples thereof include "EXL-2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1 to 3% by mass, preferably 0.2 to 2% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. The mass% is more preferable, and 0.3 to 1% by mass is further preferable.

<(G) Curing accelerator>
In one embodiment, the resin composition may contain (G) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, organic peroxide-based curing accelerators, and the like. , Phosphorus-based curing accelerator, amine-based curing accelerator, imidazole-based curing accelerator, and metal-based curing accelerator are preferable, and imidazole-based curing accelerator and organic peroxide-based curing accelerator are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

Examples of the organic peroxide-based curing accelerator include dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, and di-tert-butyl. Peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like can be mentioned. As the organic peroxide-based curing accelerator, a commercially available product may be used, and examples thereof include "Park Mill D" manufactured by NOF CORPORATION.

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 1% by mass, preferably 0.01 when the non-volatile component in the resin composition is 100% by mass. It is more preferably from% by mass to 0.5% by mass, and even more preferably from 0.01% by mass to 0.1% by mass.

<(H) Flame Retardant>
In one embodiment, the resin composition may contain (H) flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone-based flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5 to 20% by mass, preferably 0.5 to 15% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. Is more preferable, and 0.5 to 10% by mass is further preferable.

<(I) Arbitrary additive>
In one embodiment, the resin composition may further contain other additives, if necessary, and such other additives include, for example, an organic copper compound, an organic zinc compound, an organic cobalt compound and the like. Examples thereof include organometallic compounds of the above, thickeners, defoaming agents, leveling agents, adhesion-imparting agents, resin additives such as colorants, and the like.

<Physical characteristics and uses of resin composition>
The resin composition of the present invention has a low minimum melt viscosity. Further, this resin composition can provide an insulating layer having a low dielectric loss tangent, a low roughness, and a high peel strength. Therefore, the resin composition can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board), and interlayer insulation of the printed wiring board. It can be more preferably used as a resin composition for forming a layer (a resin composition for forming an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

The cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a characteristic of excellent adhesion (plating peel strength) to a conductor layer made of plating or the like. That is, it provides an insulating layer showing good plating peel strength. The plating peel strength is preferably more than 0.5 kgf / cm, more preferably 0.53 kgf / cm or more, still more preferably 0.55 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less, 1 kgf / cm or less, or the like. The plating peel strength can be measured according to the method described in <Measurement of Peel Strength (Plating Peel Strength) of Conductor Layer> described later.

A cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. That is, it provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.009 or less, more preferably 0.008 or less, still more preferably 0.007 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric loss tangent> described later.

The minimum melt viscosity of the resin composition is preferably 1000 poise or less, more preferably 800 poise or less, still more preferably 700 poise or less, from the viewpoint of suppressing cracks and circuit distortion. The lower limit of the minimum melt viscosity is preferably 50 poise or more, more preferably 100 poise or more, still more preferably 150 poise or more, from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin.

The minimum melt viscosity means the minimum viscosity exhibited by the resin composition when the resin of the resin composition is melted. Specifically, when the resin composition is heated at a constant temperature rise rate to melt the resin, the melt viscosity decreases with increasing temperature in the initial stage, and then increases with temperature increase after a certain level. .. The minimum melt viscosity means the melt viscosity of such a minimum point. The minimum melt viscosity of the resin composition can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

[Sheet-like laminated material]
The resin composition of the present invention can be applied and used in a varnished state, but industrially, it is generally preferable to use the resin composition in the form of a sheet-like laminated material containing the resin composition. As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

<Adhesive film>
In one embodiment, the adhesive film comprises a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 50 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

In the adhesive film, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can be rolled up and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

<Prepreg>
In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, still more preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but is usually 10 μm or more.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the above-mentioned adhesive film.

[Manufacturing method of printed wiring board and printed wiring board]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed by a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is a wiring layer). be).

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The thickness of the insulating layer between the first and second conductor layers is the insulation between the main surface 11 of the first conductor layer 1 and the main surface 21 of the second conductor layer 2, as shown by an example in FIG. It refers to the thickness t1 of the layer 3. The first and second conductor layers are adjacent conductor layers via an insulating layer, and the main surface 11 and the main surface 21 face each other.

The thickness t2 of the entire insulating layer is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, or 10 μm or less. The lower limit is not particularly limited, but is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned adhesive film.
(I) A step of laminating the resin composition layer of the adhesive film on the inner layer substrate so as to be bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, or the like, or one or both sides of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, an inner layer circuit board as an intermediate product on which an insulating layer and / or a conductor layer should be formed when the printed wiring board is manufactured is also included in the "inner layer board" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The inner layer substrate and the adhesive film can be laminated, for example, by heat-pressing the adhesive film to the inner layer substrate from the support side. Examples of the member for heat-pressing the adhesive film to the inner layer substrate (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the adhesive film, but to press it through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the adhesive film may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

After laminating, the laminated adhesive film may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and step (II) or after step (II).

In step (II), the resin composition layer is thermoset to form an insulating layer.

The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 170 ° C. The curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the support is removed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form the multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling solution used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing liquid can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing liquid at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

Since the printed wiring board of the present invention contains an insulating layer formed of a cured product of the resin composition of the present invention, the roughness can be lowered. In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening the cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes is preferably 150 nm. Below, it is more preferably 125 nm or less, still more preferably 100 nm or less. The lower limit is not particularly limited, but may be 10 nm or more, 50 nm or more, or the like. The arithmetic mean roughness (Ra) can be measured, for example, according to the method described in <Measurement of Arithmetic Mean Roughness (Ra)> described later.

Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. The step (V) is a step of forming the second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed of a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper layer is preferable. A metal layer is more preferred.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired printed wiring board design.

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example of forming the conductor layer by the semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

Since the adhesive film of the present invention provides an insulating layer having good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured by using the adhesive film of the present invention has an embodiment including an insulating layer which is a cured product of the resin composition layer of the adhesive film and an embedded wiring layer embedded in the insulating layer. May be good.

In another embodiment, the printed wiring board can be manufactured using the prepreg described above. The manufacturing method is basically the same as when an adhesive film is used.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip in manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up layer. Examples thereof include a mounting method using (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation of sample for measuring peel strength and arithmetic mean roughness (Ra value)>
(1) Base treatment of inner layer circuit board Both sides of glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A”) on which the inner layer circuit is formed. Was etched by 1 μm with “CZ8101” manufactured by MEC to roughen the copper surface.

(2) Lamination of Adhesive Films The adhesive films produced in Examples and Comparative Examples were subjected to a resin composition layer using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700). Both sides of the inner layer circuit board were laminated so as to be bonded to the inner layer circuit board. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of Resin Composition After laminating the adhesive film, the resin composition layer was heat-cured at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to form an insulating layer. Then, the support was peeled off to expose the insulating layer.

(4) Roughing treatment The inner layer circuit board with the exposed insulating layer is immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes. Then, soak in an oxidizing agent (Atotech Japan's "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass) at 80 ° C. for 20 minutes, and finally inside. It was immersed in a Japanese solution (“Reduction Solution Securigant P” manufactured by Atotech Japan, aqueous solution of hydroxylamine sulfate) at 40 ° C. for 5 minutes. Then, it was dried at 80 ° C. for 15 minutes. The obtained substrate is referred to as "evaluation substrate a".

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, the conductor layer was formed by performing a plating step (copper plating step using a chemical solution manufactured by Atotech Japan Co., Ltd.) including the following steps 1 to 6.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
The surface of the evaluation substrate a was washed with Cleaning Cleaner Security 902 (trade name) at 60 ° C. for 5 minutes.
2. Soft etching (cleaning inside the via hole)
The surface of the evaluation substrate a was treated with an aqueous solution of sodium sulfate-acidic peroxodisulfate at 30 ° C. for 1 minute.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
The surface of the evaluation substrate a was changed to Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
The surface of the evaluation substrate a was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (Pd applied to the insulating layer is reduced)
The surface of the evaluation substrate a was subjected to Reducer Neoganth WA (trade name) and Reducer Acceralator 810 modding. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
A mixture of Basic Solution Printed MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35 ° C. The surface of the evaluation substrate a was treated for 20 minutes to form an electroless plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

Then, after heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. to form a conductor layer having a thickness of 30 μm, and annealing treatment was performed at 200 ° C. for 60 minutes. The obtained substrate is referred to as "evaluation substrate b".

<Measurement of Arithmetic Mean Roughness (Ra)>
Regarding the evaluation substrate a obtained by the (4) roughening treatment, the measurement range was 121 μm × 92 μm by using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by Becoin Sturments) in VSI contact mode and a 50x lens. The Ra value of the surface of the insulating layer was determined from the numerical value obtained as. It was measured by calculating the average value of 6 randomly selected points.

<Measurement of peel strength (plating peel strength) of conductor layer>
The peel strength of the insulating layer and the conductor layer was measured for the evaluation substrate b in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a notch having a width of 10 mm and a length of 100 mm is made in the conductor layer of the evaluation substrate b, one end of the notch is peeled off, and the conductor layer is grasped with a gripper. The load (kgf / cm) when the 35 mm was peeled off was measured, and the peeling strength was determined. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.

<Measurement of minimum melt viscosity>
The minimum melt viscosity of the resin composition layer in the adhesive films produced in Examples and Comparative Examples was measured. Using "Rheosol-G3000" manufactured by UBM, using a parallel plate with a resin amount of 1 g and a diameter of 18 mm, the starting temperature is from 60 ° C to 200 ° C, the temperature rise rate is 5 ° C / min, and the measurement temperature. The minimum melt viscosity was measured under the measurement conditions of an interval of 2.5 ° C. and a vibration of 1 Hz / deg.

<Measurement of dielectric loss tangent>
The adhesive films produced in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes to heat-cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as "evaluation cured product c". The cured product c for evaluation was cut into test pieces having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured using "HP8362B" manufactured by Agilent Technologies, Inc. at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method. Measurements were made on the two test pieces, and the average value was calculated.

<Measurement of epoxy resin viscosity>
The viscosity (25 ° C) of the monofunctional epoxy resin having a biphenyl structure and some epoxy resins is an E-type viscometer (using "RE-25U" manufactured by Toki Sangyo, 1 ° 34'x R24 cone rotor). Was measured at 25 ° C. and 20 rpm.

<Example 1>
Monofunctional epoxy resin with biphenyl structure ("SY-OPG" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent about 230, viscosity 205 mPa · s) 30 parts, naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent 332) ) 30 parts were dissolved by heating in 55 parts of solvent naphtha with stirring, and then cooled to room temperature. 260 parts of spherical silica (average particle size 0.5 μm, Admatex “SO-C2”) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) and methacrylic butadiene in the mixed solution. Three parts of styrene rubber particles (“EXL-2655” manufactured by Dow Chemical Japan, Inc.) were added and kneaded with three rolls to uniformly disperse them. To the roll dispersion, 40 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223, a toluene solution having a non-volatile component of 65% by mass), a phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Co., Ltd.), 40 parts of MEK with a solid content of 30% by mass (1: 1 solution of cyclohexanone), curing accelerator ("DMAP", 4-dimethylaminopyridine, methyl ethyl ketone solution with a solid content of 5% by mass (hereinafter abbreviated as "MEK")) Six parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 1.

As a support, a PET film released with an alkyd resin-based mold release agent (Lintec's "AL-5") (Toray's "Lumira R80", thickness 38 μm, softening point 130 ° C, "release PET") I prepared. Resin varnish 1 is uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying is 40 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 5 minutes. , Adhesive film 1 was produced.

<Example 2>
In Example 1, 14 parts of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, a hydroxyl group equivalent of about 151, and a 2-methoxypropanol solution having a solid content of 50%) was further mixed with the roll dispersion. bottom. A resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1 except for the above items.

<Example 3>
In Example 2, 30 parts of naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 332) was changed to 30 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185). bottom. A resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 2 except for the above items.

<Example 4>
In Example 2, 30 parts of naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 332) was changed to 30 parts of naphthylene ether type epoxy resin (“HP6000” manufactured by DIC Corporation, epoxy equivalent of about 213). bottom. A resin varnish 4 and an adhesive film 4 were produced in the same manner as in Example 2 except for the above items.

<Example 5>
In Example 2, 40 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223, a toluene solution of 65% by mass of a non-volatile component) was added to a phenol novolac type polyfunctional cyanate ester resin (Lonza Japan). The company's "PT30", cyanate equivalent 124) was changed to 26 copies. A resin varnish 5 and an adhesive film 5 were produced in the same manner as in Example 2 except for the above items.

<Comparative example 1>
In Example 1, 30 parts of a monofunctional epoxy resin having a biphenyl structure (“SY-OPG” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent of about 230) was used as a naphthalene type bifunctional epoxy resin (“HP4032D” manufactured by DIC Corporation, epoxy equivalent). Approximately 140, viscosity 2593 mPa · s) was changed to 30 parts. Except for the above items, the resin varnish 6 and the adhesive film 6 were produced in the same manner as in Example 1.

<Comparative example 2>
In Example 1, 30 parts of a monofunctional epoxy resin having a biphenyl structure (“SY-OPG” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent of about 230) was used as a bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent). Approximately 180, viscosity 2000 mPa · s) 30 parts. A resin varnish 7 and an adhesive film 7 were produced in the same manner as in Example 1 except for the above items.

<Comparative example 3>
In Example 1, 30 parts of a monofunctional epoxy resin having a biphenyl structure (“SY-OPG” manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., epoxy equivalent of about 230) was used as a cyclohexane type epoxy resin (“ZX1658GS” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent). Approximately 135, viscosity 34 mPa · s) was changed to 30 parts. A resin varnish 8 and an adhesive film 8 were produced in the same manner as in Example 1 except for the above items.

It has been confirmed that in Examples 1 to 5, even when the components (C) to (G) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

1 First conductor layer 11 Main surface of the first conductor layer 2 Second conductor layer 21 Main surface of the second conductor layer 3 Insulation layer t1 Spacing between the first conductor layer and the second conductor layer (first And the thickness of the insulating layer between the second conductor layers)
t2 Thickness of the entire insulating layer

Claims (12)

It contains (A) a monofunctional epoxy resin having a biphenyl structure, (B) a curing agent, and (D) epoxy resin other than the component (A).
The content of the component (A) is 1% by mass or more and 20% by mass or less when the non-volatile component in the resin composition is 100% by mass.
The component (D) contains an epoxy resin having two or more epoxy groups in one molecule.
A resin composition for forming an insulating layer of a printed wiring board, wherein the content of the component (D) is 1% by mass or more and 20% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein the component (A) is a compound represented by the following general formula (1).

(In the formula, R represents a single bond or a divalent linking group.) R in the general formula (1) has an oxygen atom, a sulfur atom, -NH-, -C (= O)-, -SO-, an alkylene group which may have a substituent, and a substituent. The resin composition according to claim 2, which represents a optionally arylene group or a group consisting of a combination of two or more thereof. The resin composition according to claim 2 or 3, wherein R in the general formula (1) represents a group composed of a combination of an oxygen atom and an alkylene group which may have a substituent. The resin composition according to any one of claims 1 to 4, wherein the component (A) is the following compound.

The resin composition according to any one of claims 1 to 5, wherein the component (B) is selected from a phenol-based curing agent, a cyanate ester-based curing agent, and an active ester-based curing agent. The resin composition according to any one of claims 1 to 6, further comprising (C) an inorganic filler. The resin composition according to claim 7, wherein the content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. A sheet-like laminated material for forming an insulating layer of a printed wiring board, which comprises the resin composition for forming an insulating layer of the printed wiring board according to any one of claims 1 to 8. A support, provided on the support, and a any one resin composition which is formed of an insulating layer forming resin composition of the printed wiring board according to paragraph layer of claims 1-8, printing Adhesive film for forming an insulating layer on a wiring board. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 11.

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