JP2019044097A - Resin composition - Google Patents

Abstract

To provide a resin composition capable of providing a well-balanced cured product which, even when a large amount of inorganic filler is used, can maintain adhesion between the cured product and a conductor layer after an environmental test under high temperature and high humidity environment.SOLUTION: The resin composition contains (A) an epoxy resin, (B) a benzoxazine compound, and (C) inorganic filler, where the component (B) is represented by the following general formula (B-1) and, when a non-volatile component in the resin composition is assumed to be 100 mass%, a content of the component (C) is 67 mass% or more. In formula (B-1), Rrepresents an n-valent group containing an oxygen atom; R's each independently represent 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.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, it is related with the resin sheet, printed wiring board, and semiconductor device which are obtained using the said resin composition.

  As a technique for manufacturing a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a 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 trisphenolmethane. Patent Document 2 contains a polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D), and the active ester compound (B) Disclosed is 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 as the equivalent ratio of phenolic hydroxyl group / active ester group. ing.

JP 2012-171968 A JP 2014-148562 A

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

  An object of the present invention is to obtain a well-balanced cured product that can maintain adhesion between a conductor layer after an environmental test under a high-temperature and high-humidity environment even when a large amount of an inorganic filler is used. The present invention provides a resin composition; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed using the resin composition; and a semiconductor device.

  In order to achieve the object of the present invention, as a result of intensive studies, the present inventors have made it possible to include a specific benzoxazine compound in the resin composition even after using an inorganic filler in a large amount. However, it has been found that the adhesion between the conductor layer and the insulating layer can be maintained. Moreover, in addition to said adhesiveness, it discovered that it was excellent also in the smear removal property, and came to complete this 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 comprising (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler,
(B) component is represented by the following general formula (B-1),
(C) The resin composition whose content of a component is 67 mass% or more when the non-volatile component in a resin composition is 100 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 nonvolatile 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 nonvolatile 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], in which 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 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 formed of the resin composition according to any one of [1] to [9] provided on the support.
[11] The resin sheet according to [10], wherein the resin composition layer has a thickness of 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 inorganic filler is used, a well-balanced cured product that can maintain adhesion between the conductor layer after an environmental test under a high temperature and high humidity environment can be obtained. A resin composition; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed 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, resin sheet, printed wiring board, and 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, wherein the component (B) has the following general formula (B-1 The content of the component (C) is 67% by mass or more when the nonvolatile 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 nonvolatile component in the resin composition is 100% by mass, a specific benzoxazine compound is contained in a high temperature and high humidity environment. Even after the environmental test, it is possible to maintain the adhesion between the conductor layer and to obtain a cured product having excellent smear removability. And normally, the hardened | cured material which can maintain high adhesiveness even after the environmental test in a high-temperature, high-humidity environment can exhibit high adhesiveness over a long period of time.

  Conventionally, it is known that the (B) benzoxazine compound functions as a curing agent for epoxy resins. However, the present inventors use a large amount of an inorganic filler or include a specific benzoxazine compound so that the conductor layer and the insulating layer are not separated even after an environmental test under a high temperature and high humidity environment. It was found that the adhesiveness of can be maintained. Moreover, in addition to the said adhesiveness, it discovered that it was excellent also in the smear removal property. By containing a specific benzoxazine compound, even if a large amount of inorganic filler is used, even after an environmental test in a high-temperature and high-humidity environment, high adhesion is maintained and smear removal is excellent. As far as the present inventors are aware, it can be said that no specific 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 ( H) An optional additive may be included. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
The resin composition includes (A) an epoxy resin. Examples of (A) epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol types. Epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin , Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin Heterocyclic epoxy resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  (A) The epoxy resin is preferably an aromatic epoxy resin 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 is preferably a bisphenol A type epoxy resin or bisphenol. It is preferable to use either an F-type epoxy resin or a naphthol-type epoxy resin.

  (A) The epoxy resin preferably has two or more epoxy groups in one molecule. When the nonvolatile 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. In particular, the resin composition is a combination of an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter also referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (also referred to as “solid epoxy resin”). It is preferable to include. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a 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”, “Epicoat” manufactured by Mitsubishi Chemical Corporation. 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" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX, manufactured by Daicel Corporation "Celoxide "021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy resin), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include bixylenol 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, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and 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), “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 Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical Company “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), “jER1010” manufactured by Mitsubishi Chemical Corporation (solid) Bisuf Nord A-type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  (A) As a component, when using together a liquid epoxy resin and a solid epoxy resin, those quantity ratios (liquid epoxy resin: solid epoxy resin) are the mass ratio, and are the range of 1: 1-1: 20. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 1 to 1:15. The range of 1: 1 to 1:10 is more preferable.

The content of the component (A) in the resin composition is preferably 5 masses when the nonvolatile component in the resin composition is 100 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, and further preferably 15% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of (A) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  (A) The weight average molecular weight of a component becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene 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 a (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. Examples of such a group include an n-valent group comprising a combination of an oxygen atom and an arylene group, an n-valent group comprising a combination of an oxygen atom and an alkylene group, and a combination of an oxygen atom, an arylene group and an alkylene group. n-valent group, etc., and includes a combination of oxygen atom and arylene group from the viewpoint of improving the adhesion between the insulating layer and the conductor layer after the environmental test and effectively improving the smear removability. 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 more preferable. Specific examples of the alkylene group include a methylene group, an ethylene group, and a propylene group, 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, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- 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 _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

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 further 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 further preferably an aryl group having 6 to 10 carbon atoms. A halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkyl group and 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, an integer of 2 to 3 is preferable, and 2 is more preferable. m represents an integer of 0 to 4, an integer of 0 to 3 is preferable, and 0 is more preferable.

  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 General Formula (B-2) is preferably at least one of the benzoxazine compounds represented by General Formula (B-3) and 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. For example, when a benzoxazine compound represented by the general formula (B-3) and a benzoxazine compound represented by the general formula (B-4) are used as a mixture, a mass mixing ratio (general formula (B-3) : General formula (B-4)) is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and more preferably 1: 3 to 3: 1. By making 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. Furthermore, it is usually possible to effectively improve smear removability.

  (B) Specific examples of the benzoxazine compound include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical; “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd .; “HFB2006M” manufactured by Showa Polymer Co., Ltd. Etc.

  (B) The molecular weight of the benzoxazine compound 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, from the viewpoint of improving adhesion. Preferably it is 500 or less.

  The content of the (B) benzoxazine compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably 1% by mass when the nonvolatile component in the resin composition is 100% by mass. % Or more. An upper limit becomes like this. Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less or 3 mass% or less. By making content of (B) component into such a range, the adhesiveness of the insulating layer and conductor layer after an environmental test can be improved. Furthermore, it is usually possible to effectively improve smear removability.

<(C) Inorganic filler>
The resin composition contains (C) an inorganic filler. (C) From the viewpoint of reducing the coefficient of thermal expansion, the content of the inorganic filler is 67% by mass or more, preferably 68% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. Preferably it is 70 mass% or more. An upper limit becomes like this. Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. In the present invention, since (B) the benzoxazine compound is contained, it is possible to maintain the adhesion after the HAST test even when (C) the inorganic filler is contained by 67 mass% or more.

  (C) The material of the inorganic filler is not particularly limited as long as it is an inorganic compound. 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, titanate Examples include magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. It is. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  (C) Examples of commercially available inorganic fillers include “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; “YC100C”, “YA050C”, and “YA050C-MJE” manufactured by Admatechs. "YA010C"; Denka's "UFP-30"; Tokuyama's "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N"; Admatechs' "SC2500SQ" “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. (C) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.5 μm or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 5.0 micrometers or less, More preferably, it is 2.0 micrometers or less, More preferably, it is 1.0 micrometers or less. In addition, (C) the average particle size of the inorganic filler is in the above range, so that the circuit embedding property of the resin composition layer is usually improved, the surface roughness of the insulating layer is reduced, (C) The inorganic filler can be easily filled.

  (C) The average particle diameter 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 preparing a particle size distribution of (C) inorganic filler on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus and setting the median diameter as an 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 particle size distribution measuring device, “LA-500” manufactured by Horiba, “SALD-2200” manufactured by Shimadzu, etc. can be used.

  (C) The inorganic filler may be surface-treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, and a titanate coupling agent. . Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry 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. A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The degree of the 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, 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 more preferable from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the sheet form. preferable.

  (C) The amount of carbon per unit surface area of the inorganic filler can be measured after (C) the inorganic filler after the surface treatment is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler (C) surface-treated with the surface treatment agent, and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount 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. can be used.

<(D) Active ester compound>
In one embodiment, the resin composition may contain (D) an active ester compound. It is known that when an active ester compound is used, the smear removal property is usually inferior. However, since the hardened | cured material of the resin composition of this invention is excellent in smear removal property, even if it uses an active ester compound, smear removal property is not inferior.

  Although there is no restriction | limiting in particular as an active ester compound, Generally ester groups with high reaction activity, such as ester of phenol ester, thiophenol ester, N-hydroxyamine ester, and heterocyclic hydroxy compound, are generally in 1 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 preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  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 a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As an active ester compound having a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000H-65TM” are commercially available as active ester compounds. , “EXB-8000L-65TM”, “EXB-8150-65T” (manufactured by DIC), “EXB9416-70BK” (manufactured by DIC) as an active ester compound containing a naphthalene structure, and 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 benzoylated product of phenol novolac, and an active ester compound which is an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation), and “YLH1048” (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoylated phenol novolacs Etc.

  When the resin composition contains (D) the active ester compound, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of 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 still more preferably 1: 0.1 to 1: 1.5. Here, the reactive group of the active ester compound is an active ester group. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the active ester compound is The value obtained by dividing the solid content mass of each active ester compound by the reactive group equivalent is the total value for all active ester compounds. By making the quantity ratio of an epoxy resin and an active ester compound into such a range, the heat resistance of the hardened | cured material of a resin composition improves more.

  When the resin composition contains (D) an active ester compound, the content of the component (D) is preferably 1% by mass or more, more preferably 2%, when the nonvolatile component in the resin composition is 100% by mass. It is at least 3% by mass, more preferably at least 3% by mass. 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 setting the content of the component (D) within such a range, the peel strength before and after the environmental test can be improved.

<(E) Curing agent>
In one embodiment, the resin composition may contain (E) a curing agent. However, (D) active ester compound is not included in (E) curing agent. (E) Curing agent is not particularly limited as long as it has a function of curing component (A). For example, phenolic curing agent, naphthol curing agent, cyanate ester curing agent, and carbodiimide curing. Agents and the like. Among these, from the viewpoint of improving the insulation reliability, the (E) curing agent is preferably one or more of a phenolic curing agent, a naphthol curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. More preferably, a phenolic curing agent is included. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  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. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | 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-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), 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 Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester 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 dicyanate is triazine-modified into a trimer), and the like.

  Specific examples of the carbodiimide 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 and the curing agent is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range of 1: 0.01 to 1: 2 is preferable, 1: 0.03 to 1: 3 is more preferable, and 1: 0.05 to 1: 1.5 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  When the resin composition contains (D) an active ester compound and (E) a curing agent, the amount ratio of the epoxy resin to the active ester compound is [total number of epoxy groups of epoxy resin]: [(D) and ( E) Total number of reactive groups in component] 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 preferred. By making the quantity ratio of an epoxy resin, (D) component, and (E) component into such a range, the heat resistance of the hardened | cured material of a resin composition improves more.

  When the resin composition contains (E) a curing agent, the content of (E) the curing agent is preferably 0.1% by mass or more when the nonvolatile component in the resin composition is 100% by mass, Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. An upper limit becomes like this. Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less. (E) By making content of a hardening | curing agent into such a range, the adhesiveness of an insulating layer and a 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 a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator is more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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'-undecylimidazolyl- (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-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2. -Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. 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, and zinc stearate.

  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 when the nonvolatile component in the resin composition is 100% by mass. Is 0.05 mass% or more, more preferably 0.1 mass% or more. An upper limit becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less. By setting the content of the curing accelerator within such a range, it is possible to obtain a cured product that is particularly excellent in 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. (G) 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. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  (G) The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably 38000 or more, more preferably 40000 or more, and further preferably 42000 or more. An upper limit becomes like this. Preferably it is 100,000 or less, More preferably, it is 70000 or less, More preferably, it is 60000 or less. (G) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, (G) the weight average molecular weight in terms of polystyrene of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L manufactured by Showa Denko KK 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 the mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. 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” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by NS ”,“ YL6794 ”,“ YL7213 ”,“ YL7290 ”,“ YL7482 ”, and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC 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 “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include 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), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

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

  Specific examples of the polyethersulfone 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.

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

  Especially, as a (G) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among these, 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 nonvolatile component in the resin composition is 100% by mass, More preferably, it is 0.2 mass% or more, More preferably, it is 0.3 mass% or more. An upper limit becomes like this. Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less. (G) By setting the content of the thermoplastic resin within such a range, a cured product that is particularly excellent in adhesion after an environmental test in a high-temperature and high-humidity environment when a large amount of inorganic filler is used is obtained. Can do.

<(H) Optional additive>
In one embodiment, the resin composition may further contain other additives as necessary. Examples of such other additives include a flame retardant, an organic filler, an organic copper compound, an organic compound, and the like. Examples thereof include organometallic compounds such as zinc compounds and organic cobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

  Examples of the flame retardant include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-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”, “SPE-100” manufactured by Otsuka Chemical Co., Ltd., “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd. “FP-110”, “FP-300”, “FP-400” and the like can be mentioned, and as the flame retardant other than the phosphazene compound, a commercially available product may be used, for example, “HCA-HQ” manufactured by Sanko Co., Ltd. And “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.

  As the organic filler, any organic filler that can be used in 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 Aika Industry.

<Physical properties and uses of resin composition>
The cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes, 170 ° C. for 30 minutes, and then at 200 ° C. for 90 minutes usually has a copper foil peeling strength (peel strength) before the environmental test (HAST test). Shows excellent properties. That is, an insulating layer having excellent adhesion before the environmental test is brought about. 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 peel 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 usually has a characteristic of excellent copper foil peeling strength (peel strength) after an environmental test. Show. That is, it provides an insulating layer that has excellent adhesion after an environmental test and can exhibit high adhesion over 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, and further 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 the property of being excellent in smear removability. 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 obtained. 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 that is excellent in thin-film insulation and can maintain adhesion between the conductor layer after an environmental test under a high-temperature and high-humidity environment. Therefore, the resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, It can use more suitably as a resin composition (resin composition for interlayer insulation layers of a printed wiring board) for forming an insulating layer. Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed 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, and even more preferably from the viewpoint that the printed wiring board can be thinned and a cured product having excellent insulation can be provided even if it is a thin film. It is 10 μm or less, or 8 μm or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, 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.). It may be used.

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film according to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). It is done. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to suppress adhesion and scratches of dust and the like on the surface of the resin composition layer.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol, etc. Carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  The resin sheet can be stored in a roll. 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 the resin composition layer) that can maintain adhesion between the thin film insulating property and the conductive layer after an environmental test under 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. Therefore, it can be used more suitably as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). Moreover, 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, By forming the insulating layer with a resin sheet, the distance between the first and second conductor layers (the 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 wiring board]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of 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 from the second conductor layer (the conductor layer is referred to as a wiring layer). is there).

  Since an insulating layer is formed with the hardened | cured material of the resin composition of this invention, it is excellent in thin film insulation. For this reason, 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, and even 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 (the thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown in FIG. 11 and the thickness t 1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2. The first and second conductor layers are conductor layers adjacent to each other via an insulating layer, and the main surface 11 and the main surface 21 face each other.

  The total thickness t2 of the insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less. Although it does not specifically limit about a minimum, Usually, it can be set as 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in the step (I) is a member that becomes a printed wiring board substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate. Etc. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Further, when the printed wiring board is manufactured, an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

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

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is preferably 120 ° C to 240 ° C, more preferably 150 ° C to 220 ° C, and further preferably 170 ° C to 200 ° C. ° C. The curing time is 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 formed 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, and further preferably 15 minutes to 100 minutes).

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, 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.

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. 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 liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in 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. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 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 oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be set to 1 nm or more. Further, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be set to 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type 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. When the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. 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. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or 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 nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer 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.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by a method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  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. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an 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 a good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board. The component built-in circuit board can be manufactured by a known manufacturing method.

  A printed wiring board manufactured using the resin sheet of the present invention is an aspect including an insulating layer that is a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer. Also 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 using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  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 location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless buildup layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following description, “parts” and “%” representing amounts 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) was dissolved in 40 parts of solvent naphtha with stirring. This was cooled to room temperature, and (A) the melt | dissolution composition of the epoxy resin was prepared. Further, 5 parts of a benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was heated and dissolved in 5 parts of MEK with stirring, and further cooled to room temperature to prepare a solution of (B) a benzoxazine compound. .

  (A) 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass), phenolic resin having a triazine skeleton and a novolak structure Hardener (“LA-3018-50P” manufactured by DIC, 2-methoxypropanol solution having an active group equivalent of about 151 and solid content of 50%), active ester compound (“HPC-8000-65T” manufactured by DIC, activity 50 parts by weight of a base equivalent of about 223 and a solid content of 65% by weight toluene solution, 5 parts of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution having a solid content of 10% by weight), an amine-based alkoxysilane compound (Spherical silica surface-treated with “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Admatechs Co. "SO-C2") 250 parts, and (B) were mixed solution of 10 parts of benzoxazine compounds, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

  A polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared as a support. On the release layer of this support, the resin varnish was uniformly applied so that the resin composition layer after drying had a thickness of 25 μm. Thereafter, the resin varnish was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to obtain a resin sheet including 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) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave for 20 minutes. Using a laser diffraction 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, 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”). “Toluene / MEK mixed solution having an active group equivalent of 220 and a solid content of 65%) was changed to 50 parts. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Example 3]
In Example 1, 50 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, 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”). "Toluene solution having an active group equivalent of 230 and a solid content of 60%). Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 1]
In Example 1, 250 parts of spherical silica (average particle size 0.77 μm, Admatex “SO-C2”) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) To 240 parts, and the benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was not used. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 2]
In Example 2, 250 parts of spherical silica (average particle size 0.77 μm, Admatex “SO-C2”) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) To 240 parts, and the benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was not used. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Comparative Example 3]
In Example 3, 250 parts of spherical silica (average particle size 0.77 μm, Admatex “SO-C2”) surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) To 240 parts, and the benzoxazine compound (“JBZ-OP100D” manufactured by JFE Chemical Co., Ltd.) was not used. Except for the above, a resin varnish and a resin sheet were produced in the same manner as in Example 1.

[Evaluation method]
The resin sheet obtained by the Example and comparative example which were mentioned above was evaluated by the following method.

<Measurement of peel strength>
(Production of evaluation substrate)
(1) Base treatment of interior substrate:
A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R1515A” manufactured by Panasonic Corporation) having a copper foil on the surface was prepared as an inner layer substrate. All the copper foil on the surface of the inner layer substrate was removed by etching. Thereafter, drying was performed at 190 ° C. for 30 minutes.

(2) Lamination of resin sheets:
Using the batch-type vacuum pressure laminator (Nikko Materials, Inc. 2-stage buildup laminator “CVP700”), the resin composition layer obtained from the above-described Examples and Comparative Examples was used as the inner layer substrate. Lamination was performed on both sides of the inner layer substrate so as to be bonded. This lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at a temperature of 100 ° C. and a pressure of 0.74 MPa.
Next, the laminated resin sheet was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Thereafter, the support was peeled off to obtain an “intermediate multilayer I” including 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 Kinzoku Co., Ltd.) was prepared. The glossy surface of this copper foil was etched using a microetching agent (“CZ8101” manufactured by MEC) with a copper etching amount of 1 μm to perform a roughening treatment. The copper foil thus obtained is referred to as “roughened copper foil”.

  This roughened copper foil was laminated on both surfaces of the intermediate multilayer body I such 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 lamination was performed under the same conditions as those for laminating the resin sheet on the inner layer substrate described above. Thereby, "intermediate multilayer 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.

  This intermediate multilayer body II 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. Next, the intermediate multilayer body II was taken out of the oven to be in a room temperature atmosphere, and was then put into an oven at 200 ° C. and further heated for 90 minutes. Thus, the resin composition layer is thermally cured, and the roughened copper foil, the insulating layer as the cured product of the resin composition layer, the inner layer substrate, the insulating layer as the cured product of the resin composition layer, and the roughened An “evaluation substrate A” including the copper foil in this order was obtained. In this evaluation substrate 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 according to JIS C6481. Specifically, the peel strength was measured by the following operation.

  The roughened copper foil of the evaluation board A was cut to enclose a rectangular part having a width of 10 mm and a length of 100 mm. One end of the rectangular portion was peeled off and held by a gripping tool (manufactured by TS E, Autocom type tester “AC-50C-SL”). A range of 35 mm in length of the rectangular part was peeled off in the vertical direction, and the load (kgf / cm) at the time of peeling was measured as the peel strength before the HAST test. The peeling was performed at a speed of 50 mm / min at room temperature.

(Measurement of peel strength after environmental test (HAST test))
Thereafter, a HAST test was performed 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 removability>
(1) Base treatment of interior substrate:
A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R1515A” manufactured by Panasonic Corporation) having a copper foil on the surface was prepared as an inner layer substrate. The copper foil on the surface of the inner layer substrate was etched using a microetching agent (“CZ8101” manufactured by MEC) with a copper etching amount of 1 μm to perform a roughening treatment. Thereafter, drying was performed at 190 ° C. for 30 minutes.

(2) Lamination and curing of resin sheets:
Using the batch-type vacuum pressure laminator (Nikko Materials, Inc. 2-stage buildup laminator “CVP700”), the resin composition layer obtained from the above-described Examples and Comparative Examples was used as the inner layer substrate. Lamination was performed on both sides of the inner layer substrate so as to be bonded. This lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at a temperature of 100 ° C. and a pressure of 0.74 MPa.

  Next, the laminated resin sheet was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. 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) Via hole formation:
Use Via Mechanics, Ltd. CO ₂ laser processing machine (LK-2K212 / 2C), the pulse width 3μ seconds at a frequency 2000 Hz, the output 0.95 W, by processing the insulating layer under the conditions of the shot number 3, the insulating layer surface 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. Further, the support was peeled off to obtain a circuit board.

(4) Roughening treatment:
The insulating layer surface of the circuit board was immersed at 60 ° C. for 10 minutes in a swelling dip securigant P manufactured by Atotech Japan, which is a swelling liquid. Next, the insulating layer surface of the circuit board was immersed in a concentrated liquid P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan for 25 minutes at 80 ° C. . Finally, the insulating layer surface of the circuit board was immersed at 40 ° C. for 5 minutes in a reduction solution securigant P manufactured by Atotech Japan, which is a neutralizing solution.

(5) Residue evaluation at bottom of via hole:
The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), 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-described examples and comparative examples are shown in the following table. In the following table, the amount of each component represents a non-volatile component conversion amount. In the table below, the meanings of the abbreviations are as follows.
ESN475V: naphthol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330)
ZX1059: bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169)
JBZ-OP100D: benzoxazine compound (manufactured by JFE Chemical)
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 Admatechs)
EXB8150-60T: active ester compound (manufactured by DIC, toluene solution having an active group equivalent of 230 and a solid content of 60%)
EXB8000L-65TM: Active ester compound (manufactured by DIC, toluene / MEK mixed solution having an active group equivalent of 220 and a solid content of 65%)
HPC-8000-65T: active ester compound (manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass)
LA-3018-50P: a phenolic curing agent having a triazine skeleton and a novolak structure (manufactured by DIC, 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 having a solid content of 10% by mass)
YX7553BH30: Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass)

  In Examples 1 to 3, it was confirmed that even if the components (D) to (F) were not contained, the results were the same as those in the above Examples although there was a difference in the degree.

DESCRIPTION OF SYMBOLS 1 1st conductor layer 11 Main surface 2 of 1st conductor layer 2nd conductor layer 21 Main surface of 2nd conductor layer 3 Insulating layer t1 Space | interval (1st conductor layer and 1st conductor layer) And the thickness of the insulating layer between the second conductor layers)
t2 Total thickness of insulating layer

Claims (13)

A resin composition comprising (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler,
(B) component is represented by the following general formula (B-1),
(C) The resin composition whose content of a component is 67 mass% or more when the non-volatile component in a resin composition is 100 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.   (B) The resin composition of Claim 1 whose content of a component is 0.1 to 10 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition according to claim 1, further comprising (D) an active ester compound.   (D) The resin composition of Claim 3 whose content of a component is 5 mass% or more when the non-volatile component in a resin composition is 100 mass%.   (C) The resin composition of any one of Claims 1-4 whose average particle diameter of an inorganic filler is 0.5 micrometer or more. The resin composition according to any one of claims 1 to 5, wherein R ^{1 in the} general formula (B-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 insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating layer of a printed wiring board.   The resin sheet containing a support body and the resin composition layer formed with the resin composition of any one of Claims 1-9 provided on this support body.   The resin sheet according to claim 10, wherein the resin composition layer has a thickness of 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 printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 9.   A semiconductor device comprising the printed wiring board according to claim 12.

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