JP6870544B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique for printed wiring boards, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 discloses a thermosetting resin composition containing 50 to 99% by mass of benzoxazine and 50 to 1% by mass of trisphenol methane. Further, Patent Document 2 contains a polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D). A curable resin composition in which the ratio of the active ester group to the phenolic hydroxyl group of the benzoxazine compound (C) is 0.3 to 0.9 in the equivalent ratio of the phenolic hydroxyl group / active ester group is disclosed. ing.

Japanese Unexamined Patent Publication No. 2012-171968 Japanese Unexamined Patent Publication No. 2014-148562

In general, it is known that the adhesiveness of the conductor layer tends to decrease in a resin composition containing a large amount of an inorganic filler. As a result of further studies, the present inventors have found that a resin composition containing a larger amount of inorganic filler adheres to the conductor layer even after an environmental test (HAST test) in a high temperature and high humidity environment. It was found that the property deteriorates and it becomes difficult to maintain the adhesion for a long period of time. Especially in printed wiring boards, in order to eliminate the mismatch of the coefficient of thermal expansion between the conductor layer and the insulating layer, more inorganic filler may be added, and it is important to maintain the adhesion after the environmental test. Become.

An object of the present invention is that even if a large amount of an inorganic filler is used, a well-balanced cured product capable of maintaining adhesion with a conductor layer after an environmental test in a high temperature and high humidity environment can be obtained. It is an object of the present invention to provide a resin composition; a resin sheet containing the resin composition; 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 achieve the object of the present invention, even if a large amount of inorganic filler is used, the resin composition contains a specific benzoxazine compound after the environmental test. However, it was found that the adhesion between the conductor layer and the insulating layer can be maintained. Further, they have found that they are excellent in smear removal property in addition to the above-mentioned adhesion, and have completed the present invention.

式（Ｂ−１）中、Ｒ^１は酸素原子を含有するｎ価の基を表し、Ｒ^２はそれぞれ独立にハロゲン原子、アルキル基、又はアリール基を表す。ｎは２〜４の整数を表し、ｍは０〜４の整数を表す。
［２］ （Ｂ）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、０．１質量％以上１０質量％以下である、［１］に記載の樹脂組成物。
［３］ 更に、（Ｄ）活性エステル化合物を含む、［１］又は［２］に記載の樹脂組成物。
［４］ （Ｄ）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、５質量％以上である、［３］に記載の樹脂組成物。
［５］ （Ｃ）無機充填材の平均粒径が、０．５μｍ以上である、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ 一般式（Ｂ−１）中、Ｒ^１は酸素原子とアリーレン基との組み合わせからなるｎ価の基である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ 一般式（Ｂ−１）中、ｍは０を表す、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ プリント配線板の絶縁層形成用である、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ プリント配線板の層間絶縁層形成用である、［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］ 支持体と、該支持体上に設けられた［１］〜［９］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、樹脂シート。
［１１］ 樹脂組成物層の厚みが２５μｍ以下である、［１０］に記載の樹脂シート。
［１２］ 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］〜［９］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。
［１３］ ［１２］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler.
The component (B) is represented by the following general formula (B-1).
The content of the component (C) is 67% by mass or more when the non-volatile component in the resin composition is 100% by mass.

In formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.
[2] The resin composition according to [1], wherein the content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], further comprising (D) an active ester compound.
[4] The resin composition according to [3], wherein the content of the component (D) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[5] The resin composition according to any one of [1] to [4], wherein (C) the average particle size of the inorganic filler is 0.5 μm or more.
^{[6] The resin composition according to any one of [1] to [5], wherein R 1} is an n-valent group composed of a combination of an oxygen atom and an arylene group in the general formula (B-1).
[7] The resin composition according to any one of [1] to [6], wherein m represents 0 in the general formula (B-1).
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer of a printed wiring board.
[9] The resin composition according to any one of [1] to [8], which is used for forming an interlayer insulating layer of a printed wiring board.
[10] A resin sheet 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 [9].
[11] The resin sheet according to [10], wherein the thickness of the resin composition layer is 25 μm or less.
[12] 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 [9].
[13] A semiconductor device including the printed wiring board according to [12].

According to the present invention, even if a large amount of an inorganic filler is used, a well-balanced cured product capable of maintaining adhesion with a conductor layer can be obtained after an environmental test in a high temperature and high humidity environment. A resin composition; a resin sheet containing the resin 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 resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

式（Ｂ−１）中、Ｒ^１は酸素原子を含有するｎ価の基を表し、Ｒ^２はそれぞれ独立にハロゲン原子、アルキル基、又はアリール基を表す。ｎは２〜４の整数を表し、ｍは０〜４の整数を表す。 [Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler, and the component (B) is the following general formula (B-1). ), And the content of the component (C) is 67% by mass or more when the non-volatile component in the resin composition is 100% by mass.

In formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.

In the present invention, even if the inorganic filler is used in a large amount of 67% by mass or more when the non-volatile component in the resin composition is 100% by mass, it is contained in a specific benzoxazine compound under a high temperature and high humidity environment. Even after the environmental test in (1), the adhesion between the conductor layer and the conductor layer can be maintained, and a cured product having excellent smear removal property can be obtained. And, usually, a cured product capable of maintaining high adhesion even after an environmental test in such a high temperature and high humidity environment can exhibit high adhesion for a long period of time.

Conventionally, it is known that the (B) benzoxazine compound functions as a curing agent for an epoxy resin. However, we have found that even with a large amount of inorganic filler, by containing a specific benzoxazine compound, between the conductor layer and the insulating layer even after an environmental test in a high temperature and high humidity environment. It was found that the adhesion of the material can be maintained. Further, it has been found that in addition to the above-mentioned adhesion, it is also excellent in smear removal property. By containing a specific benzoxazine compound, even if a large amount of inorganic filler is used, high adhesion is maintained even after an environmental test in a high temperature and high humidity environment, and the smear removal property is excellent. As far as the present inventors know, it can be said that no conventional idea has been proposed.

In addition to the components (A) to (C), the resin composition comprises (D) an active ester compound, (E) a curing agent, (F) a curing accelerator, (G) a thermoplastic resin, and (G). H) It may contain any additive. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
The resin composition contains (A) epoxy resin. Examples of the epoxy resin (A) include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and 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, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. The epoxy resin may be used alone or in combination of two or more.

As the epoxy resin (A), an aromatic epoxy resin is preferable from the viewpoint of obtaining a cured product that can maintain high adhesion even after an environmental test in a high temperature and high humidity environment, and bisphenol A type epoxy resin and bisphenol. It is preferable to use either an F-type epoxy resin or a naphthol-type epoxy resin.

The epoxy resin (A) preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin 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. Among them, the resin composition is a combination of a liquid epoxy resin at a temperature of 20 ° C. (hereinafter, also referred to as “liquid epoxy resin”) and a solid epoxy resin at a temperature of 20 ° C. (also referred to as “solid epoxy resin”). It is preferable to include the epoxy. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

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, the cyclohexane type epoxy resin, the cyclohexanedimethanol type epoxy resin, the glycidylamine type epoxy resin, and the epoxy resin having a butadiene structure are preferable, and the bisphenol A type epoxy resin and the bisphenol F type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US", "jER828EL", "825" and "Epicoat" manufactured by Mitsubishi Chemical Co., Ltd. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) , "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl) manufactured by Nippon Steel & Sumitomo Metal Corporation. Cyclohexane type epoxy resin), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and the like. 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 bixilenol type epoxy resin, naphthalene type epoxy resin, 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, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene 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" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "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), "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "YL7800" (fluoren) Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the amount ratio (liquid epoxy resin: solid epoxy resin) of them is in the range of 1: 1 to 1:20 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more in the range of 1: 1 to 1:15 in terms of mass ratio. The range of 1: 1 to 1:10 is preferable, and the range of 1: 1 to 1:10 is more preferable.

The content of the component (A) in the resin composition is preferably 5% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more, more preferably 10% by mass or more, still more preferably 15% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the component (A) 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 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.

式（Ｂ−１）中、Ｒ^１は酸素原子を含有するｎ価の基を表し、Ｒ^２はそれぞれ独立にハロゲン原子、アルキル基、又はアリール基を表す。ｎは２〜４の整数を表し、ｍは０〜４の整数を表す。 <(B) Benzoxazine compound>
The resin composition contains the (B) benzoxazine compound represented by the following general formula (B-1).

In formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4.

R ¹ represents an n-valent group containing an oxygen atom. Such groups include an n-valent group consisting of a combination of an oxygen atom and an arylene group, an n-valent group consisting of a combination of an oxygen atom and an alkylene group, and a combination of an oxygen atom, an arylene group and an alkylene group. An n-valent group or the like is mentioned, and it is composed of a combination of an oxygen atom and an arylene group from the viewpoint of improving the adhesion between the insulating layer and the conductor layer after the environmental test and from the viewpoint of effectively improving the smear removal property. It is preferably an n-valent group.

As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 12 carbon atoms is further preferable. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group and the like, and a phenylene group is preferable.
As the alkylene group, 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 3 carbon atoms is further preferable. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like, and a methylene group is preferable.

Specific examples of the n-valent group containing an oxygen atom include the following groups. In the formula, "*" represents a bond.

The arylene group and 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.

R ² independently represents a halogen atom, an alkyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. The halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group and the aryl group may have a substituent. The substituent is the same as the substituent that the arylene group may have.

n represents an integer of 2 to 4, with an integer of 2 to 3 being preferred, and 2 being more preferred. m represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0.

The benzoxazine compound represented by the general formula (B-1) is preferably a benzoxazine compound represented by the following general formula (B-2) from the viewpoint of effectively obtaining the desired effect of the present invention. ..

The benzoxazine compound represented by the general formula (B-2) is preferably at least one of the benzoxazine compounds represented by the general formula (B-3) and the general formula (B-4).

The benzoxazine compound represented by the general formula (B-1) may be used alone or as a mixture of two or more kinds. For example, when the benzoxazine compound represented by the general formula (B-3) and the benzoxazine compound represented by the general formula (B-4) are used as a mixture, the mass mixing ratio (general formula (B-3)). : The general formula (B-4)) is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and even more preferably 1: 3 to 3: 1. By setting the mass mixing ratio within such a range, the adhesion between the insulating layer and the conductor layer after the environmental test can be improved. In addition, the smear removal property can usually be effectively improved.

(B) Specific examples of the benzoxazine compound include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "FA" manufactured by Shikoku Kasei Kogyo Co., Ltd .; "HFB2006M" manufactured by Showa Polymer Co., Ltd. And so on.

The molecular weight of the benzoxazine compound (B) is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, preferably 1000 or less, more preferably 800 or less, and further, from the viewpoint of improving adhesion. It is preferably 500 or less.

The content of the benzoxazine compound (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass. % Or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less or 3% by mass or less. By keeping the content of the component (B) within such a range, the adhesion between the insulating layer and the conductor layer after the environmental test can be improved. In addition, the smear removal property can usually be effectively improved.

<(C) Inorganic filler>
The resin composition contains (C) an inorganic filler. The content of the inorganic filler (C) is 67% by mass or more, preferably 68% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of lowering the coefficient of thermal expansion. It is preferably 70% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. In the present invention, since the (B) benzoxazine compound is contained, it is possible to maintain the adhesion after the HAST test even if the (C) inorganic filler is contained in an amount of 67% by mass or more.

The material of the inorganic filler (C) is not particularly limited as long as it is an inorganic compound, and for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide. , Hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Examples thereof include magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium 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.

(C) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd .; "YC100C", "YA050C" and "YA050C-MJE" manufactured by Admatex Co., Ltd. , "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatex. "SO-C4", "SO-C2", "SO-C1"; and the like.

Usually, the (C) inorganic filler is contained in the resin composition in the form of particles. The average particle size of the inorganic filler (C) is preferably 0.01 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.5 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. Further, when the average particle size of the (C) inorganic filler is within the above range, usually, the circuit embedding property of the resin composition layer is improved, the surface roughness of the insulating layer is reduced, and a large amount is used. (C) The inorganic filler can be easily filled.

(C) 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 the particle size distribution of (C) 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, (C) 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.

The inorganic filler (C) may be surface-treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of the surface treatment agent include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. .. 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 surface treatment agent may be used alone or in combination of two or more.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (C) inorganic filler. Carbon content per unit surface area of the inorganic filler (C), (C) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more, and 0.2 mg / m ² or more 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 (C) inorganic filler can be measured after the surface-treated (C) 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 (C) inorganic filler surface-treated with a surface treatment agent, and ultrasonically cleaned 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 (C) 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.

<(D) Active ester compound>
In one embodiment, the resin composition may contain (D) an active ester compound. It is known that the use of an active ester compound usually results in poor smear removal. However, since the cured product of the resin composition of the present invention is excellent in smear removing property, the smear removing property is not inferior even if an active ester compound is used.

The active ester compound is not particularly limited, but generally, an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds is contained in one molecule. A compound having two or more is preferably used. The active ester compound 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 compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound 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 compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-65TM" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, an active ester containing an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylate of phenol novolac, and "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound which is an acetylated product of phenol novolac. Examples of the active ester compound which is a benzoyl compound 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.

When the resin composition contains the (D) active ester compound, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the active ester compound]. The ratio is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 3, and even more preferably 1: 0.1 to 1: 1.5. Here, the reactive group of the active ester compound is an active ester group. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and is the total number of reactive groups in the active ester compound. , The value obtained by dividing the solid content mass of each active ester compound by the reaction group equivalent is the total value for all the active ester compounds. By setting the amount ratio of the epoxy resin and the active ester compound within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains the (D) active ester compound, the content of the component (D) is preferably 1% by mass or more, more preferably 2 when the non-volatile component in the resin composition is 100% by mass. It is by mass% or more, more preferably 3% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. By keeping the content of the component (D) within such a range, the peel strength before and after the environmental test can be improved.

<(E) Hardener>
In one embodiment, the resin composition may contain (E) a curing agent. However, the (D) active ester compound is not included in the (E) curing agent. The curing agent (E) is not particularly limited as long as it has a function of curing the component (A), and is, for example, a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Examples include agents. Among them, from the viewpoint of improving insulation reliability, the (E) curing agent is preferably any one or more of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. , It is more preferable to contain a phenolic curing agent. The curing agent may be used alone or in combination of two or more.

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 Meiwa Kasei Co., Ltd., 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 , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

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. '-Etilidene diphenyl 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 part or all of bisphenol A disyanate 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.

When the resin composition contains (E) a curing agent, the amount ratio of the epoxy resin to the curing agent is the ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent]. , 1: 0.01 to 1: 2, more preferably 1: 0.03 to 1: 3, and even more preferably 1: 0.05 to 1: 1.5. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (D) active ester compound and (E) curing agent, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups in the epoxy resin]: [(D) and ( E) The total number of reactive groups of the components] is preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 3, and 1: 0.1 to 1: 1. .5 is more preferable. By setting the amount ratio of the epoxy resin to the component (D) and the component (E) within such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (E) a curing agent, the content of the (E) curing agent is preferably 0.1% by mass or more, and further, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.3% by mass or more, more preferably 0.5% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. By keeping the content of the curing agent (E) within such a range, the adhesion between the insulating layer and the conductor layer can be improved.

<(F) Curing accelerator>
In one embodiment, the resin composition may contain (F) 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, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators 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, trimethylguanidine, and the like. 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-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, 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 organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex 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.

When the resin composition contains (F) a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, when the non-volatile component in the resin composition is 100% by mass. Is 0.05% by mass or more, more preferably 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. By setting the content of the curing accelerator within such a range, it is possible to obtain a cured product having particularly excellent adhesion after an environmental test in a high temperature and high humidity environment when a large amount of inorganic filler is used.

<(G) Thermoplastic resin>
In one embodiment, the resin composition may contain (G) 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, and polycarbonate resin. , Polyether ether ketone resin, polyester resin and the like, 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 (G) thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, still more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. (G) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the (G) thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L manufactured by Showa Denko Co., Ltd. as a column. / K-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 a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. 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 in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "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 New Japan Chemical 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 oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

Among them, as the (G) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in a 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.

When the resin composition contains (G) a thermoplastic resin, the content of the (G) thermoplastic resin is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass. It is more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less. (G) By setting the content of the thermoplastic resin within such a range, a cured product having particularly excellent adhesion after an environmental test in a high temperature and high humidity environment when a large amount of inorganic filler is used can be obtained. Can be done.

<(H) Arbitrary additive>
In one embodiment, the resin composition may further contain other additives, if desired, such other additives include, for example, flame retardants, organic fillers, organocopper compounds, organics. Examples thereof include organometallic compounds such as zinc compounds and organocobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants.

Examples of the flame retardant include phosphazene compounds, organophosphorus flame retardants, organonitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides and the like. Specific examples of the phosphazene compound include, for example, "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Daihachi Chemical Industry Co., Ltd., and "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd. Examples thereof include "FP-110", "FP-300", "FP-400", and commercially available products may be used as the flame retardant other than the phosphazene compound. For example, "HCA-HQ" manufactured by Sanko Co., Ltd. , "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. and the like.

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 "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

<Physical characteristics and uses of resin composition>
The cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes has a copper foil peeling strength (peel strength) before the environmental test (HAST test). It shows the characteristic of being excellent. That is, it provides an insulating layer having excellent adhesion before the environmental test. The peel strength before the environmental test is preferably 0.5 kgf / cm or more, more preferably 0.55 kgf / cm or more, and further preferably 0.6 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The copper foil peeling strength before the environmental test can be measured by the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes has a characteristic of being excellent in copper foil peeling strength (peeling strength) after an environmental test. Shown. That is, it provides an insulating layer that has excellent adhesion after an environmental test and can exhibit high adhesion for a long period of time. The peel strength after the environmental test is preferably 0.15 kgf / cm or more, more preferably 0.2 kgf / cm or more, still more preferably 0.25 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The peel strength after the environmental test can be measured by the method described in Examples described later.

A cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes usually exhibits excellent smear removing property. That is, even if a via hole is formed in the cured product, an insulating layer having a maximum smear length of 5 μm or less at the bottom of the via hole is provided. The smear removability can be measured by the method described in Examples described later.

The resin composition of the present invention can provide an insulating layer having excellent thin film insulating properties and capable of maintaining adhesion with a conductor layer after an environmental test in a high temperature and high humidity environment. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and can be used between layers of the printed wiring board. It can be more preferably used as a resin composition for forming an insulating layer (resin composition for 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.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support and formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, still more preferably 13 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulating properties even if it is a thin film. It is 10 μm or less, or 8 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 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 leaf 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 Corporation, and "Unipee" manufactured by Unitika.

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.

In one embodiment, the resin sheet may further include other layers, if desired. Examples of such other layers include a protective film similar to the support provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). Be done. 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 suppress adhesion of dust and the like to the surface of the resin composition layer and scratches.

For the resin sheet, 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. Carbitols; aromatic hydrocarbons such as toluene and xylene; 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.

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention provides an insulating layer (cured product of a resin composition layer) capable of maintaining close contact with a conductor layer after a thin film insulating property and an environmental test in a high temperature and high humidity environment. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and forms an interlayer insulating layer of the printed wiring board. It can be more preferably used as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). Further, for example, in 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 present invention. By forming the insulating layer from the resin sheet, the distance between the first and second conductor layers (thickness of the insulating layer between the first and second conductor layers) is 6 μm or less (preferably 5.5 μm or less, more preferably. Is 5 μm or less) and has excellent thin film insulation.

[Printed circuit 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). is there).

Since the insulating layer is formed of a cured product of the resin composition of the present invention, it has excellent thin film insulating properties. Therefore, 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 distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown by an example in FIG. It refers to the thickness t1 of the insulating layer 3 between the main surface 21 of the 11 and the second conductor layer 2. 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 15 μm or less, more preferably 13 μm or less, and further preferably 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 resin sheet.
(I) A step of laminating the resin composition layer of the resin sheet 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 a member that becomes a substrate of a printed wiring board, and is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. And so on. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board". Further, an intermediate product in 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 substrate" 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 resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressing the resin sheet 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 resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The inner layer substrate and the resin sheet 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 with 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 the lamination, the laminated resin sheet 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 preferably 120 ° C. to 240 ° C., more preferably 150 ° C. to 220 ° C., still more preferably 170 ° C. to 200 ° C. ℃. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even 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 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 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 a 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 size and shape of the hole 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 solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in the neutralizing solution 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.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited, but may be preferably 0.5 nm or more, more preferably 1 nm or more, and the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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. It is preferably formed by the method. 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 resin sheet 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 resin sheet of the present invention has an embodiment including an insulating layer which is a cured product of the resin composition layer of the resin sheet and an embedded wiring layer embedded in the insulating layer. May be good.

[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 electrical 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 "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Example 1]
10 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), and naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.” , Epoxy equivalent of about 330) 50 parts was heated and dissolved in 40 parts of solven naphtha with stirring. This was cooled to room temperature to prepare a dissolution composition of (A) epoxy resin. Further, 5 parts of a benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was dissolved by heating in 5 parts of MEK with stirring, and further cooled to room temperature to prepare a solution of the (B) benzoxazine compound. ..

In this (A) epoxy resin dissolution composition, 5 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass), a triazine skeleton and a phenolic structure having a novolak structure Hardener ("LA-3018-50P" manufactured by DIC, active group equivalent about 151, 2-methoxypropanol solution having 50% solid content), 5 parts, active ester compound ("HPC-8000-65T" manufactured by DIC, active Approximately 223 base equivalent, 65 parts by mass of solid content toluene solution) 50 parts, curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution of 10% by mass solid content), amine-based epoxysilane compound 250 parts of spherical silica (average particle size 0.77 μm, "SO-C2" manufactured by Admatex) surface-treated with ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 10 parts of a solution of (B) benzoxazine compound. The mixture was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. The resin varnish was uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 25 μm. Then, the resin varnish was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to obtain a resin sheet containing a support and a resin composition layer.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco Ltd.), and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size was calculated as the median diameter.

[Example 2]
In Example 1, 50 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) was added to an active ester compound (“EXB8000L-65TM” manufactured by DIC). , A toluene / MEK mixed solution having an active group equivalent of 220 and a solid content of 65%) was changed to 50 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above items.

[Example 3]
In Example 1, 50 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) was added to an active ester compound (“EXB8150-60T” manufactured by DIC). , A toluene solution having an active group equivalent of 230 and a solid content of 60%) was changed to 55 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above items.

[Comparative Example 1]
In Example 1, the amount of spherical silica (average particle size 0.77 μm, “SO-C2” manufactured by Admatex) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was 250 parts. No benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above items.

[Comparative Example 2]
In Example 2, the amount of spherical silica (average particle size 0.77 μm, “SO-C2” manufactured by Admatex) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was 250 parts. No benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above items.

[Comparative Example 3]
In Example 3, the amount of spherical silica (average particle size 0.77 μm, “SO-C2” manufactured by Admatex) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was 250 parts. No benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above items.

[Evaluation method]
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were evaluated by the following methods.

<Measurement of peel strength>
(Preparation of evaluation board)
(1) Base treatment of interior substrate:
As the inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A”) was prepared. All the copper foil on the surface of this inner layer substrate was removed by etching. Then, it dried at 190 degreeC for 30 minutes.

(2) Lamination of resin sheets:
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were used with a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) to form a resin composition layer with the above-mentioned inner layer substrate. It was laminated on both sides of the inner layer substrate so as to be joined. This lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
Next, the laminated resin sheet was heat-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it. Then, the support was peeled off to obtain an "intermediate multilayer body I" containing the resin composition layer, the inner layer substrate, and the resin composition layer in this order.

On the other hand, a copper foil having a glossy surface (thickness 35 μm, “3EC-III” manufactured by Mitsui Mining & Smelting Co., Ltd.) was prepared. The glossy surface of the copper foil was roughened by etching with a micro-etching agent (“CZ8101” manufactured by MEC) with a copper etching amount of 1 μm. The copper foil thus obtained is called "roughened copper foil".

This roughened copper foil was laminated on both sides of the intermediate multilayer body I so that the surface of the roughened copper foil subjected to the roughening treatment was bonded to the resin composition layer of the intermediate multilayer body I. This laminating was performed under the same conditions as the laminating of the resin sheet on the inner layer substrate described above. As a result, an "intermediate multilayer body II" containing the roughened copper foil, the resin composition layer, the inner layer substrate, the resin composition layer and the roughened copper foil in this order was obtained.

The intermediate multilayer body II was put into an oven at 100 ° C. and heated for 30 minutes, and then transferred to an oven at 170 ° C. and heated for 30 minutes. Next, the intermediate multilayer body II was taken out of the oven and placed in a room temperature atmosphere, and then placed in an oven at 200 ° C. for additional heating for 90 minutes. As a result, the resin composition layer is thermally cured, and the roughened copper foil, the insulating layer as a cured product of the resin composition layer, the inner layer substrate, the insulating layer as a cured product of the resin composition layer, and the rough An "evaluation substrate A" containing a copperized copper foil in this order was obtained. In this evaluation base material A, the roughened copper foil corresponds to the conductor layer.

(Measurement of peel strength before environmental test (HAST test))
Using the evaluation substrate A, the peel strength between the roughened copper foil and the insulating layer was measured. The peel strength was measured in accordance with JIS C6481. Specifically, the peel strength was measured by the following operation.

A notch surrounding a rectangular portion having a width of 10 mm and a length of 100 mm was made in the roughened copper foil of the evaluation substrate A. One end of this rectangular portion was peeled off and grasped with a grasping tool (autocom type testing machine "AC-50C-SL" manufactured by TSE Co., Ltd.). A range of 35 mm in length of the rectangular portion was peeled off in the vertical direction, and the load (kgf / cm) at the time of this peeling was measured as the peel strength before the HAST test. The peeling was performed at a rate of 50 mm / min at room temperature.

(Measurement of peel strength after environmental test (HAST test))
Then, the evaluation substrate A was subjected to a HAST test in which the evaluation substrate A was placed in an environment of a temperature of 130 ° C. and a humidity of 85% RH for 100 hours. After this HAST test, the peel strength between the roughened copper foil of the evaluation substrate A and the insulating layer was measured by the same method as before the HAST test.

<Evaluation of smear removal>
(1) Base treatment of interior substrate:
As the inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic “R1515A”) was prepared. The copper foil on the surface of this inner layer substrate was etched with a micro-etching agent (“CZ8101” manufactured by MEC) at a copper etching amount of 1 μm to perform a roughening treatment. Then, it dried at 190 degreeC for 30 minutes.

(2) Lamination and curing of resin sheets:
The resin sheets obtained in the above-mentioned Examples and Comparative Examples were used with a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) to form a resin composition layer with the above-mentioned inner layer substrate. It was laminated on both sides of the inner layer substrate so as to be joined. This lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Next, the laminated resin sheet was heat-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it. Further, this was put into an oven at 100 ° C. and heated for 30 minutes, then transferred to an oven at 170 ° C. and heated for 30 minutes.

(3) Beer hall formation:
_{Using a CO 2} laser machine (LK-2K212 / 2C) manufactured by Via Mechanics, the insulating layer is processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μsec, an output of 0.95 W, and a number of shots of 3, on the surface of the insulating layer. A via hole having a top diameter (diameter) of 50 μm and a diameter of 40 μm on the bottom surface of the insulating layer was formed. After that, the support was peeled off to obtain a circuit board.

(4) Roughening treatment:
The surface of the insulating layer of the circuit board was immersed in a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan, at 60 ° C. for 10 minutes. Next, the surface of the insulating layer of the circuit board was immersed in a roughening liquid, Atotech Japan's Concentrate Compact P ( _{an aqueous solution of KMnO 4} : 60 g / L, NaOH: 40 g / L) at 80 ° C. for 25 minutes. .. Finally, the surface of the insulating layer of the circuit board was immersed in Atotech Japan's Reduction Solution Security P, which is a neutralizing solution, at 40 ° C. for 5 minutes.

(5) Evaluation of residue at the bottom of the via hole:
The circumference of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria.
◯: Maximum smear length is less than 5 μm ×: Maximum smear length is 5 μm or more

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the amount of each component represents the non-volatile component equivalent amount. In the table below, the meanings of the abbreviations are as follows.
ESN475V: Naftor type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 330)
ZX1059: Bisphenol type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169)
JBZ-OP100D: Benzoxazine compound (manufactured by JFE Chemical Co., Ltd.)
SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle size 0.5 μm, manufactured by Admatex Co., Ltd.)
EXB8150-60T: Active ester compound (manufactured by DIC Corporation, toluene solution with active group equivalent 230, solid content 60%)
EXB8000L-65TM: Active ester compound (manufactured by DIC, active group equivalent 220, solid content 65% toluene / MEK mixed solution)
HPC-8000-65T: Active ester compound (manufactured by DIC Corporation, toluene solution with active group equivalent of about 223 and solid content of 65% by mass)
LA-3018-50P: Phenolic curing agent having a triazine skeleton and a novolak structure (manufactured by DIC Corporation, 2-methoxypropanol solution having an active group equivalent of about 151 and a solid content of 50%).
1B2PZ: Curing accelerator (1-benzyl-2-phenylimidazole, MEK solution with a solid content of 10% by mass)
YX7553BH30: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone with a solid content of 30% by mass)

In Examples 1 to 3, it has been confirmed that even when the components (D) to (F) 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)

A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, (C) an inorganic filler, and (D) an active ester compound.
The component (B) is represented by the following general formula (B-1).
The content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass.
The content of the component (C) is 67% by mass or more when the non-volatile component in the resin composition is 100% by mass.

In formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4. A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler.
The resin composition is for forming an insulating layer of a printed wiring board.
The component (B) is represented by the following general formula (B-1).
The content of the component (B) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass.
The content of the component (C) is 67% by mass or more when the non-volatile component in the resin composition is 100% by mass.

In formula (B-1), R ¹ represents an n-valent group containing an oxygen atom, and R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2 to 4, and m represents an integer of 0 to 4. The resin composition according to claim 2, further comprising (D) an active ester compound. The resin composition according to claim 1 or 3, wherein the content of the component (D) is 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. (C) The resin composition according to any one of claims 1 to 4, wherein the average particle size of the inorganic filler is 0.5 μm or more. The resin composition according to any one of claims 1 to 5, wherein in the general formula (B-1), R ¹ is an n-valent group composed of a combination of an oxygen atom and an arylene group. The resin composition according to any one of claims 1 to 6, wherein m represents 0 in the general formula (B-1). The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and a resin composition layer formed on the support according to the resin composition according to any one of claims 1 to 8. The resin sheet according to claim 9, wherein the thickness of the resin composition layer is 25 μm or less. 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 including the printed wiring board according to claim 11.

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