JP2023052814A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of providing a well-balanced cured product which is excellent in thin film insulation properties even when an inorganic filler with a small average particle size is used, and 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 having an average particle size of 100 nm or less where, when a non-volatile component in the resin composition is assumed to be 100 mass%, a content of the component (C) is 40 mass% or more.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

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

2. Description of the Related Art As a technique for manufacturing printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. For example, in Patent Document 1, an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin and an inorganic filler are included, and when the content of the inorganic filler is 100% by mass of the non-volatile component in the resin composition, , 40% by mass or more.

JP 2016-27097 A

In general, when the thickness of the insulating layer becomes thin, it is conceivable to use an inorganic filler having a small average particle size or a large specific surface area from the viewpoint of ensuring insulation reliability. However, the present inventors have found that when an inorganic filler having a small average particle size or a large specific surface area is contained in the resin composition, after an environmental test in a high-temperature and high-humidity environment, the conductor layer and the insulating layer It was found that it is difficult to maintain the adhesion between the In particular, in order to eliminate the thermal expansion coefficient mismatch between the conductor layer and the insulating layer, it may be necessary to add more inorganic fillers. It becomes difficult. In order to meet future demands for fine wiring, it is required to maintain adhesion after an environmental test even if an inorganic filler having a small average particle size or a large specific surface area is used.

However, under the constraint of using inorganic fillers with a small average particle size or a large specific surface area, no technology has been developed to improve adhesion after environmental testing.

The object of the present invention is to provide excellent thin film insulation even when using an inorganic filler with a small average particle size or a large specific surface area, and after an environmental test in a high temperature and high humidity environment, the adhesion between the conductor layer A resin composition that can maintain a well-balanced cured product; a resin sheet containing the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device is to provide

In order to achieve the object of the present invention, as a result of intensive studies by the present inventors, even if an inorganic filler having a small average particle size or a large specific surface area is used, by including a benzoxazine compound in the resin composition, , found that the adhesion between the conductor layer and the insulating layer can be maintained even after the environmental test, and completed the present invention.

式（Ｂ－１）中、Ｒ^１は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。
［７］ 一般式（１）中、Ｒ^１はアリーレン基、アルキレン基、酸素原子、又はこれらの２以上の組み合わせからなるｎ価の基である、［６］に記載の樹脂組成物。
［８］ 一般式（１）中、ｍは０を表す、［６］又は［７］に記載の樹脂組成物。
［９］ プリント配線板の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］ プリント配線板の層間絶縁層形成用である、［１］～［９］のいずれかに記載の樹脂組成物。
［１１］ 支持体と、該支持体上に設けられた［１］～［１０］のいずれかに記載の樹脂組成物で形成された樹脂組成物層とを含む、樹脂シート。
［１２］ 樹脂組成物層の厚みが１５μｍ以下である、［１１］に記載の樹脂シート。
［１３］ 第１の導体層と、第２の導体層と、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と、を含み、第１の導体層と第２の導体層との間隔が、６μｍ以下であるプリント配線板の、該絶縁層形成用である、［１１］又は［１２］に記載の樹脂シート。
［１４］ 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
該絶縁層は、［１］～［１０］のいずれかに記載の樹脂組成物の硬化物である、プリント配線板。
［１５］ 第１導体層と第２の導体層との間隔が、６μｍ以下である、［１４］に記載のプリント配線板。
［１６］ ［１４］又は［１５］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle size of 100 nm or less,
A resin composition in which the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.
[2] A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having a specific surface area of 15 m ² /g or more,
A resin composition in which the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.
[3] The resin composition according to [1] or [2], further comprising (D) a curing agent.
[4] The description of [3], wherein the component (D) contains at least one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. of the resin composition.
[5] Any one of [1] to [4], wherein the content of component (B) is 0.1% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to .
[6] The resin composition according to any one of [1] to [5], wherein component (B) is represented by the following general formula (B-1).

In formula (B-1), R ¹ represents an n-valent group, and each R ² independently represents a halogen atom, an alkyl group, or an aryl group. n represents an integer of 2-4 and m represents an integer of 0-4.
[7] The resin composition according to [6], wherein in general formula (1), R ¹ is an arylene group, an alkylene group, an oxygen atom, or an n-valent group consisting of a combination of two or more thereof.
[8] The resin composition according to [6] or [7], wherein m represents 0 in general formula (1).
[9] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer of a printed wiring board.
[10] The resin composition according to any one of [1] to [9], which is used for forming an interlayer insulating layer of a printed wiring board.
[11] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [10] provided on the support.
[12] The resin sheet of [11], wherein the resin composition layer has a thickness of 15 µm or less.
[13] A first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein the first conductor layer and the second conductor layer The resin sheet according to [11] or [12], which is for forming the insulating layer of a printed wiring board having a distance of 6 μm or less from the conductor layer.
[14] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of [1] to [10].
[15] The printed wiring board according to [14], wherein the distance between the first conductor layer and the second conductor layer is 6 μm or less.
[16] A semiconductor device comprising the printed wiring board according to [14] or [15].

According to the present invention, even if an inorganic filler with a small average particle size or a large specific surface area is used, the thin film insulation is excellent, and after an environmental test in a high temperature and high humidity environment, the adhesion between the conductor layer A resin composition that can maintain a well-balanced cured product; a resin sheet containing the resin composition; a printed wiring board provided with 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.

[Resin composition]
The first resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle size of 100 nm or less, wherein (C ) component is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass. The second resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having a specific surface area of 15 m ² /g or more. , the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass. By containing (B) the benzoxazine compound, the resin compositions of the first and second embodiments have excellent thin film insulation even when using an inorganic filler having a small average particle size or a large specific surface area. Moreover, it is possible to obtain a cured product that can maintain adhesion to the conductor layer even after an environmental test in a high-temperature and high-humidity environment. Generally, a cured product that can maintain high adhesion even after an environmental test in a high-temperature and high-humidity environment can exhibit high adhesion over a long period of time.

Conventionally, (B) a benzoxazine compound is known to function as a curing agent for epoxy resins. However, the present inventors found that when an inorganic filler having an average particle size of 100 nm or less or an inorganic filler having a specific surface area of 15 m ² /g or more and a benzoxazine compound are combined, It has been found that the adhesion between the conductor layer and the insulating layer can be maintained even after environmental testing under the hood. As far as the present inventors know, the technical idea of maintaining high adhesion even after an environmental test in a high-temperature and high-humidity environment by including a benzoxazine compound has never been proposed. It can be said that

In addition to the components (A) to (C), the resin composition optionally contains (D) a curing agent, (E) a curing accelerator, (F) a thermoplastic resin, (G) a flame retardant, and (H ) may contain optional additives. Hereinafter, each component contained in the resin composition of the first and second embodiments of the present invention will be described in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as "resin composition".

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. (A) Epoxy resins include, for example, 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 type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples include dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type 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) 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, such as bisphenol A type epoxy resin, bisphenol It is preferable to use either AF type epoxy resin or biphenyl type epoxy resin.

(A) The epoxy resin preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. Among them, the resin composition includes an epoxy resin that is liquid at a temperature of 20° C. (hereinafter also referred to as a “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter also referred to as a “solid epoxy resin”). are preferably included in combination. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups per molecule, more preferably an aromatic liquid epoxy resin having two or more epoxy groups per molecule. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, glycidylamine-type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A-type epoxy resin is more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, and "828US", "jER828EL", "825", and "Epikote" 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) , Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Nagase ChemteX Co., Ltd. "EX-721" (glycidyl ester type epoxy resin), Daicel Co., Ltd. "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1,4-glycidyl cyclohexane type epoxy resin), Mitsubishi Chemical Corporation "630LSD" (glycidylamine type epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak 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 bixylenol type epoxy resin and bisphenol AF type epoxy resin are preferable. more preferred. Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" ( cresol novolak type epoxy resin), "N-695" (cresol novolak 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 novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" ( naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) , “YX8800” (anthracene type epoxy resin), “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals Co., Ltd., “YL7760” manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin), “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Corporation's "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used together as component (A), the ratio by weight (liquid epoxy resin: solid epoxy resin) is in the range of 1:1 to 1:20. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) when used in the form of a resin sheet, moderate adhesiveness is provided, and ii) when used in the form of a resin sheet. iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:1 to 1:5 by mass. Preferably, the range of 1:1 to 1:3 is more preferred.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of component (A) in the resin composition is preferably 10% by mass when the non-volatile component in the resin composition is 100% by mass. % or more, more preferably 15 mass % or more, and still more preferably 20 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of component (A) is preferably 50 to 5,000, more preferably 50 to 3,000, even more preferably 80 to 2,000, still more preferably 110 to 1,000. Within this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

The weight average molecular weight of component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

<(B) Benzoxazine compound>
The resin composition contains (B) a benzoxazine compound. The (B) benzoxazine compound is a compound having a benzoxazine ring represented by the following formula (B-2) in the molecule.

(B) The number of benzoxazine rings per molecule of the benzoxazine compound is preferably 1 or more, more preferably 1 or more, more preferably from the viewpoint of improving high adhesion even after an environmental test in a high-temperature, high-humidity environment. It is 2 or more, preferably 10 or less, more preferably 5 or less.

(B) The benzoxazine compound preferably has an aromatic ring in addition to the benzoxazine ring. By having an aromatic ring in addition to the benzoxazine ring, high adhesion can be maintained even after an environmental test under a higher temperature and humidity environment. Aromatic rings include benzene ring, naphthalene ring, anthracene ring, biphenyl ring and the like, and benzene ring is preferred. In addition, the number of aromatic rings is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of improving the adhesion.

式（Ｂ－１）中、Ｒ^１は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。 As the benzoxazine compound (B), a benzoxazine compound represented by the following general formula (B-1) is preferable.

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

R ¹ represents an n-valent group. Such a group is preferably an arylene group, an alkylene group, an oxygen atom, or an n-valent group consisting of a combination of two or more thereof, and an arylene group or an n-valent group consisting of a combination of two or more. is more preferred, and an n-valent group consisting of a combination of two or more is even more preferred.

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 even more preferable. Specific examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group and the like, with a phenylene group being preferred.
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 even more preferable. Specific examples of the alkylene group include, for example, a methylene group, an ethylene group, a propylene group and the like, and a methylene group is preferred.

Examples of the group consisting of a combination of two or more include, for example, a group in which one or more arylene groups and one or more oxygen atoms are bonded, a group in which one or more arylene groups and one or more alkylene groups are bonded, and one or more alkylene groups. A group in which one or more oxygen atoms are bonded to a group, a group in which one or more arylene groups, one or more alkylene groups, and one or more oxygen atoms are bonded, and the like, and one or more arylene groups and one or more oxygen atoms. A group in which an atom is bonded and a group in which one or more arylene groups and one or more alkylene groups are bonded are preferable. Specific examples of the group consisting of a combination of two or more include the following groups. In the formula, "*" represents a bond.

An arylene group and an alkylene group may have a substituent. The substituents are not particularly limited, and examples thereof include halogen atoms, —OH, —O—C _1-6 alkyl groups, —N(C _1-6 alkyl groups) ₂ , C _1-6 alkyl groups, C _{6- 10} aryl group, —NH ₂ , —CN, —C(O)O—C _1-6 alkyl group, —COOH, —C(O)H, —NO ₂ and the like. Here, the term “C _p−q ” (where p and q are positive integers and satisfies p<q) means that the organic group described immediately after this term has p to q carbon atoms. represents something. For example, the expression "C _1-6 alkyl group" indicates an alkyl group having from 1 to 6 carbon atoms.

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

Each ^R2 independently represents a halogen atom, an alkyl group, or an aryl group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms. A halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Alkyl groups and aryl groups may have substituents. The substituent is the same as the substituent that the arylene group may have.

n represents an integer of 2 to 4, preferably an integer of 2 to 3, more preferably 2. m represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0.

The benzoxazine compound represented by the general formula (B-1) is a benzoxazine compound represented by the following general formulas (B-3) and (B-4) from the viewpoint of obtaining the desired effects of the present invention. It is preferable that it is at least one of.

The benzoxazine compound represented by the general formula (B-3) is preferably at least one of the benzoxazine compounds represented by the general formulas (B-5) and (B-6), and the general formula The benzoxazine compound represented by (B-4) is preferably a benzoxazine compound represented by general formula (B-7).

The benzoxazine compound represented by the general formula (B-1) may be used singly or as a mixture of two or more. For example, when the benzoxazine compound represented by the general formula (B-5) and the benzoxazine compound represented by the general formula (B-6) are used as a mixture, the mass mixing ratio (general formula (B-5) : general formula (B-6)) is preferably 1:10 to 10:1, more preferably 1:5 to 5:1, and more preferably 1:3 to 3:1. By setting the mass mixture ratio within this range, the adhesion to the conductor layer after the environmental test can be improved.

(B) Specific examples of benzoxazine compounds include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical; "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo; "HFB2006M" manufactured by the company.

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

(B) The content of the benzoxazine compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass when the non-volatile component in the resin composition is 100% by mass. % or more. The upper limit is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less or 3% by mass or less. By setting the content of the component (B) within this range, the adhesion to the conductor layer after the environmental test can be improved.

<(C) Inorganic filler>
The first resin composition contains (C) an inorganic filler having an average particle size of 100 nm or less. Moreover, the resin composition of the second embodiment contains (C) an inorganic filler having a specific surface area of 15 m ² /g or more. These inorganic fillers may be collectively referred to simply as "(C) inorganic fillers".

(C) The material of the inorganic filler is not particularly limited as long as it is an inorganic compound, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, and zinc oxide. , hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, titanic acid Examples include magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of (C) the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less from the viewpoint of thin film insulation. Although the lower limit of the average particle diameter is not particularly limited, it may be preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more.
In addition, the average particle size of the inorganic filler in the second embodiment is preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less from the viewpoint of thin film insulation. Although the lower limit of the average particle diameter is not particularly limited, it may be preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more.
Examples of commercial products of the (C) inorganic filler having such an average particle size include “UFP-30” manufactured by Denki Kagaku Kogyo.

(C) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler (C) is prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter thereof can be used as the average particle size for measurement. As the measurement sample, one obtained by dispersing (C) the inorganic filler in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction/scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

The specific surface area of the inorganic filler in the second embodiment is preferably 15 m ² /g or more, more preferably 20 m ² /g or more, still more preferably 30 m ² /g or more, from the viewpoint of thin film insulation. Although there is no particular upper limit, it is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and even more preferably 40 m ² /g or less.
Moreover, the specific surface area of the inorganic filler in the first embodiment is preferably 15 m ² /g or more, more preferably 20 m ² /g or more, still more preferably 30 m ² /g or more, from the viewpoint of thin film insulation. Although there is no particular upper limit, it is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and even more preferably 40 m ² /g or less.
The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method.

(C) The inorganic filler may be surface-treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. . 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 Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane). One type of surface treatment agent may be used alone, or two or more types may be used in combination.

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

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

(C) The content of the inorganic filler is 40% by mass or more, preferably 45% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, from the viewpoint of improving thin film insulation. Preferably, it is 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. In the present invention, since (B) the benzoxazine compound is contained, even if the (C) inorganic filler is contained in an amount of 40% by mass or more, the adhesion after the HAST test can be maintained.

<(D) Curing agent>
In one embodiment, the resin composition may contain (D) a curing agent. The curing agent (D) is not particularly limited as long as it has a function of curing the component (A). Examples include phenol curing agents, naphthol curing agents, active ester curing agents, and cyanate ester curing agents. and carbodiimide-based curing agents. Among them, from the viewpoint of improving insulation reliability, the (D) curing agent is any one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. It is preferable that it is above, and it is more preferable that it contains a phenol-based curing agent. A single curing agent may be used alone, or two or more curing agents may be used in combination.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" 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. ”, DIC “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like.

The active ester curing agent is not particularly limited, but in general, one molecule of an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. A compound having two or more in it is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H- 65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and as an active ester compound containing an acetylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolak, and "DC808" (Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated phenol novolac (manufactured by Mitsubishi Chemical Corporation), and active ester-based curing agents that are benzoyl compounds of phenol novolak include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation). .

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resins) and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.

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

The ratio of the epoxy resin to the curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], and is preferably in the range of 1:0.01 to 1:2. 1:0.05 to 1:3 is more preferred, and 1:0.1 to 1:1.5 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. Further, the total number of epoxy groups in the epoxy resin is the sum of the values 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 in the curing agent is It is a value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent and totaling all the curing agents. By setting the ratio between the epoxy resin and the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

(D) When a curing agent is contained, the content of (D) curing agent is preferably 1% by mass or more, more preferably 3% by mass or more, when the non-volatile component in the resin composition is 100% by mass. More preferably, it is 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. (D) By setting the content of the curing agent within this range, the adhesion to the conductor layer can be improved.

<(E) Curing accelerator>
In one embodiment, the resin composition may contain (E) a curing accelerator. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and amine-based curing accelerators are more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

Examples of imidazole curing accelerators 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'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Guanidine curing accelerators include, for example, 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] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper 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; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.03%, when the non-volatile component in the resin composition is 100% by mass. It is at least 0.05% by mass, more preferably at least 0.05% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. By setting the content of the curing accelerator within this range, even if an inorganic filler with a small average particle size or a large specific surface area is used, curing with excellent adhesion after an environmental test in a high-temperature and high-humidity environment can be achieved. can get things.

<(F) Thermoplastic resin>
In one embodiment, the resin composition may contain (F) a thermoplastic resin. (F) Thermoplastic resins include, for example, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyetheretherketone resin, polyester resin, etc., and phenoxy resin is preferred. The thermoplastic resin may be used singly or in combination of two or more.

(F) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, and even more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less. (F) The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin (F) is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. as a column. /K-804L can be calculated by using chloroform or the like as a mobile phase, measuring the column temperature at 40° C., and using a standard polystyrene calibration curve.

Examples of phenoxy resins 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, and terpene. and a phenoxy resin having 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 phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" (bisphenolacetophenone). skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; ”, “YL6794”, “YL7213”, “YL7290” and “YL7482”.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and Sekisui. S-lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Kagaku Kogyo Co., Ltd. may be mentioned.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like.

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

Among them, the (F) thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Accordingly, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, a phenoxy resin is preferable as the thermoplastic resin, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

When the resin composition contains (F) a thermoplastic resin, the content of the (F) thermoplastic resin is preferably 0.1% by mass or more when the non-volatile component in the resin composition is 100% by mass, More preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. (F) By setting the content of the thermoplastic resin within such a range, even if an inorganic filler having a small average particle size or a large specific surface area is used, the adhesion strength after an environmental test in a high temperature and high humidity environment It is possible to obtain a cured product excellent in

<(G) Flame Retardant>
In one embodiment, the resin composition may contain (G) a flame retardant. (G) Flame retardants include, for example, phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides, with phosphazene compounds being preferred. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

The phosphazene compound is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group.

Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100" and "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 "SPH-100" manufactured by Otsuka Chemical Co., Ltd. is preferable.

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

When the resin composition contains (G) a flame retardant, the content of the (G) flame retardant is preferably 0.3% by mass or more, more preferably 100% by mass of non-volatile components in the resin composition. is 0.5% by mass or more, more preferably 0.7% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

<(H) Optional Additives>
In one embodiment, the resin composition may further contain other additives as necessary, such other additives include, for example, organic fillers, organic copper compounds, organic zinc compounds and Examples include organometallic compounds such as organocobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

Any organic filler that can be used in forming the insulating layer of a printed wiring board may be used as the organic filler, and examples thereof include rubber particles, polyamide fine particles, silicone particles, and the like. Commercially available rubber particles may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd., and the like.

<Physical properties and applications of the resin composition>
A cured product obtained by thermally curing the resin composition at 100° C. for 30 minutes and then at 180° C. for 30 minutes usually has excellent insulating properties even if the thickness is 5.0±0.5 μm. Even though it is a thin film, it exhibits excellent insulation resistance (thin film insulation). The insulation resistance value of the cured product having a thickness of 5±0.5 μm is preferably 1×10 ⁷ Ω or more, more preferably 1×10 ⁸ Ω or more, and still more preferably 1×10 ⁹ Ω or more. Although the upper limit is not particularly limited, it may be 100×10 ¹² Ω or less. The insulation resistance value can be measured by the method described in Examples below. When component (B) reacts with component (A), phenolic hydroxyl groups are generated from component (B), and these phenolic hydroxyl groups suppress oxidation of metals such as copper during environmental tests. As a result, it is believed that the cured product of the resin composition of the present invention has improved adhesion after the environmental test.

A cured product obtained by thermally curing a resin composition at 190° C. for 90 minutes usually exhibits excellent copper foil peeling strength (adhesion) before an environmental test. That is, it provides an insulating layer with excellent adhesion before the environmental test. The copper foil peel strength before the environmental test is preferably 0.45 kgf/cm or more, more preferably 0.50 kgf/cm or more, and still more preferably 0.55 kgf/cm or more. Although the upper limit is not particularly limited, it 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 below.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes usually exhibits excellent copper foil peeling strength (adhesion) after an environmental test. That is, it provides an insulating layer that exhibits excellent adhesion after an environmental test and can exhibit high adhesion over a long period of time. The copper foil peel strength after the environmental test is preferably 0.20 kgf/cm or more, more preferably 0.21 kgf/cm or more, and still more preferably 0.25 kgf/cm or more. Although the upper limit is not particularly limited, it may be 10 kgf/cm or less. The copper foil peel strength after the environmental test can be measured by the method described in Examples below.

INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide an insulating layer that has excellent thin-film insulating properties and can maintain adhesion to a conductor layer after an environmental test in a high-temperature, high-humidity environment. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on an insulating layer (resin for forming an insulating layer for forming a conductor layer composition), can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board. (resin composition for interlayer insulating layer of printed wiring board). Moreover, since the resin composition of the present invention provides an insulating layer having good part-embedding properties, it can be suitably used when the printed wiring board is a component-embedded circuit board.
Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention is used as an insulating layer for forming a rewiring layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for semiconductor chip sealing). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

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

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 13 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulation even if it is a thin film. It is 10 μm or less, or 8 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, or 2 μm or more.

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 sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, 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" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Such other layers include, for example, a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

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

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; 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 carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies 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, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

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

The resin sheet of the present invention provides an insulating layer (cured product of a resin composition layer) that can maintain thin-film insulation properties and adhesion to a conductor layer after an environmental test in a high-temperature and high-humidity environment, even if it is thin. . 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 forming an interlayer insulating layer of a printed wiring board. It can be more suitably used as a resin sheet (resin sheet for an interlayer insulation layer of a printed wiring board) for the purpose. Further, for example, in a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, the 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 5.5 μm or less). is 5 μm or less), and excellent thin film insulation can be obtained.

[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 from the cured 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 sometimes called a wiring layer). be).

Since the insulating layer is formed from the cured product of the resin composition of the present invention, it has excellent thin film insulating properties. Therefore, the thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, even more preferably 5 μm or less. Although the lower limit is not particularly limited, it 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, as shown in FIG. 11 and the thickness t1 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 with an insulating layer interposed therebetween, and the main surfaces 11 and 21 face each other.

The thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less. Although the lower limit is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

A printed wiring board can be manufactured using the resin sheet described above by a method including the following steps (I) and (II).
(I) Step of laminating the resin composition layer of the resin sheet on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

The support may be removed between steps (I) and (II) or 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 conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and still more preferably 170° C. to 200° C. °C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 90 minutes.

Before thermosetting the resin composition layer, 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 cured at a temperature of 50° C. or higher and less than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

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

Step (III) is a step of making holes 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 to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

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

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 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 surface roughness meter.

Step (V) is a step of forming a conductor layer. When no conductor layer is formed on the inner layer substrate, the step (V) is a step of forming a first conductor layer, and when a conductor layer is formed on the inner layer substrate, the conductor layer becomes the first conductor layer. and step (V) is a step of forming a second conductor layer.

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

The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds 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.

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

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 the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

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

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

A printed wiring board manufactured using the resin sheet of the present invention is provided with 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. good too.

[Semiconductor device]
A 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 semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (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 bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.
In addition, Example 3 and Example 8 shall be read as Reference Example 3 and Reference Example 8, respectively. The same applies to Table 1 below.

[Preparation of resin composition]
<Example 1: Preparation of resin composition 1>
Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "828US", epoxy equivalent of about 180) 10 parts, biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent of about 190) 20 parts, and bisphenol AF type epoxy resin ( Mitsubishi Chemical "YL7760", epoxy equivalent about 238) 10 parts, phosphazene resin (Otsuka Chemical "SPH-100") 3 parts, phenoxy resin (Mitsubishi Chemical "YL7553BH30", MEK with a solid content of 30% by mass and cyclohexanone) was heated and dissolved in 60 parts of MEK with stirring.

After cooling to room temperature, 30 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, an active group equivalent of about 223, a toluene solution with a solid content of 65% by mass), a phenolic curing agent (manufactured by DIC "LA-3018-50P", active group equivalent about 151, solid content 50% 2-methoxypropanol solution) 16 parts, benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co.) 3 parts, curing accelerator (4 -Dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 4 parts, spherical silica surface-treated with an amine-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573") (manufactured by Denki Kagaku Kogyo "UFP-30", average particle size 0.078 μm, specific surface area 30.7 m ² /g) were mixed, uniformly dispersed in a high-speed rotating mixer, and then filtered through a cartridge filter ("SHP020" manufactured by ROKITECHNO). Thus, a resin composition 1 was produced.

<Example 2: Preparation of resin composition 2>
In Example 1, the amount of the benzoxazine compound (“ODA-BOZ” manufactured by JFE Chemical Co., Ltd.) was changed from 3 parts to 15 parts. A resin composition 2 was produced in the same manner as in Example 1 except for the above matters.

<Example 3: Preparation of resin composition 3>
In Example 1, 3 parts of a benzoxazine compound (“ODA-BOZ” manufactured by JFE Chemical Co., Ltd.) was changed to 3 parts of a benzoxazine compound (“Pd” manufactured by Shikoku Kasei Co., Ltd.). A resin composition 3 was prepared in the same manner as in Example 1 except for the above matters.

<Example 4: Preparation of resin composition 4>
In Example 1, 30 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass) was added to an active ester curing agent (manufactured by DIC "EXB9416-70BK", an active group equivalent of about 274, a MIBK (methyl isobutyl ketone) solution with a solid content of 70% by mass) was changed to 28 parts. A resin composition 4 was produced in the same manner as in Example 1 except for the above matters.

<Example 5: Preparation of resin composition 5>
In Example 1, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent weight: about 216, solid content: 50% by mass, toluene solution) was added. A resin composition 5 was prepared in the same manner as in Example 1 except for the above matters.

<Example 6: Preparation of resin composition 6>
In Example 1, 30 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution with a solid content of 65% by mass) was added to a naphthol curing agent (Nippon Steel & Sumikin Chemical Co., Ltd. "SN485", active group equivalent about 215) 7.2 parts, phenolic curing agent (DIC "LA-3018-50P", active group equivalent about 151, solid content 50% 2-methoxypropanol solution ), 16 parts of phenol-based curing agent (DIC "LA-7054", active group equivalent of about 124, solid content of 60% MEK solution) 12 parts, amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. 110 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ² /g) surface-treated with 100 parts. A resin composition 6 was prepared in the same manner as in Example 1 except for the above matters.

<Example 7: Preparation of resin composition 7>
In Example 6, the amount of the benzoxazine compound (“ODA-BOZ” manufactured by JFE Chemical Co., Ltd.) was changed from 3 parts to 15 parts. A resin composition 7 was produced in the same manner as in Example 6 except for the above matters.

<Example 8: Preparation of resin composition 8>
In Example 6, 3 parts of a benzoxazine compound (“ODA-BOZ” manufactured by JFE Chemical Co., Ltd.) was changed to 3 parts of a benzoxazine compound (“Pd” manufactured by Shikoku Kasei Co., Ltd.). A resin composition 8 was produced in the same manner as in Example 6 except for the above matters.

<Comparative Example 1: Production of resin composition 9>
In Example 1, spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.078 μm, specific surface area 30 .7 m ² /g), spherical silica (average particle diameter 0.77 μm, specific surface area 5.9 m ² /g, Admatechs "SO-C2") was changed to 110 parts. A resin composition 9 was produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 2: Production of resin composition 10>
In Example 6, spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.078 μm, specific surface area 30 .7 m ² /g) was coated with spherical silica (average particle diameter 0.77 μm, specific surface area 5.9 m ² /g, "SO-C2" manufactured by Admatechs) was changed to 100 parts. A resin composition 10 was produced in the same manner as in Example 6 except for the above matters.

<Comparative Example 3: Production of resin composition 11>
In Example 1, 3 parts of the benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co.) was not added. A resin composition 11 was produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 4: Production of resin composition 12>
In Example 6, 3 parts of a benzoxazine compound ("ODA-BOZ" manufactured by JFE Chemical Co.) was not added. A resin composition 12 was produced in the same manner as in Example 6 except for the above matters.

<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 into a vial and dispersed by ultrasonic waves for 20 minutes. Using a laser diffraction particle size distribution analyzer ("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.

[Production of resin sheet]
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., hereinafter “release PET” released with an alkyd resin release agent (“AL-5” manufactured by Lintec Co., Ltd.) There is a thing called.) was prepared.

<Preparation of resin sheet A>
Each resin composition is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 15 μm, and dried at 80 ° C. for 3 minutes. A resin composition layer was obtained. Next, on the surface of the resin composition layer that is not bonded to the release PET, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is attached to the resin composition layer. It was laminated so as to join. As a result, a resin sheet A was obtained which consisted of the release PET (support), the resin composition layer, and the protective film in that order.

<Production of resin sheet B>
Each resin composition is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 6 μm, and dried at 80 ° C. for 1 minute. A resin composition layer was obtained. Next, on the surface of the resin composition layer that is not bonded to the support, a rough surface of a polypropylene film (manufactured by Oji F-Tex Co., Ltd. "Alphan MA-411", thickness 15 μm) as a protective film is bonded to the resin composition layer. It was laminated so as to As a result, a resin sheet B was obtained, which consisted of the release PET (support), the resin composition layer, and the protective film in that order.

[Measurement of Copper Foil Peeling Strength]
<Preparation of sample>
(1) Surface treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in MEC Etch Bond “CZ-8101” manufactured by MEC Co., Ltd. to roughen the copper surface. (Ra value = 1 µm), and an antirust treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130° C. for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer Peel off the protective film from each resin sheet A prepared in advance, and use a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.) to form a resin composition layer. The laminate is bonded to a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) on which an inner layer circuit is formed. Laminated on both sides. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. The release PET as the support was peeled off from the laminated resin sheet. The treated surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as above. Then, a sample was produced by curing the resin composition layer under curing conditions of 190° C. for 90 minutes to form an insulating layer.

<Measurement of copper foil peel strength (adhesion 1)>
The prepared samples were cut into 150 x 30 mm pieces. Using a cutter, cut the copper foil portion of the small piece with a width of 10 mm and a length of 100 mm. AC-50C-SL"), and using an Instron universal testing machine, at room temperature, the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min was measured in accordance with JIS C6481. .

<Measurement of copper foil peel strength (adhesion 2) after environmental test (HAST)>
The prepared sample was subjected to an accelerated environmental test (environmental test) for 100 hours under conditions of 130° C. and 85% RH using a highly accelerated life tester (“PM422” manufactured by Kusumoto Kasei Co., Ltd.). After that, as in the measurement of adhesion 1, one end of the copper foil was peeled off and gripped with a gripper (manufactured by TSE Co., Autocom type testing machine, "AC-50C-SL"), and the Instron universal test Using a machine, the load was measured in accordance with JIS C6481 when a 35 mm strip was vertically peeled off at a speed of 50 mm/min at room temperature.

In addition, when the measurement result in the adhesion 2 was less than 0.20 kgf/cm, it was evaluated as "x", and when it was 0.20 kgf/cm or more, it was evaluated as "good".

[Measurement of thickness of insulating layer between conductor layers and insulation reliability of insulating layer]
(Preparation of substrate for evaluation)
(1) Surface treatment of inner layer circuit board As the inner layer circuit board, glass cloth base epoxy resin both sides having circuit conductors (copper) formed with a wiring pattern of L/S (line/space) = 2 µm/2 µm on both sides A copper-clad laminate (thickness of copper foil: 3 μm, substrate thickness: 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size: 255×340 mm) was prepared. Both surfaces of the laminate were subjected to an organic coating treatment on the copper surface using "FlatBOND-FT" manufactured by MEC.

(2) Lamination of resin sheets The protective film is peeled off from each resin sheet B prepared in advance, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) is used to form a resin composition layer. was laminated on both sides of the laminate so that the was in contact with the laminate. Lamination was carried out by pressure bonding for 45 seconds at 130° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an atmospheric pressure of 13 hPa or less. Then, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The laminate with the resin sheet laminated thereon is placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C for 30 minutes and then heat-cured to a thickness of 5 μm. was formed, and the release PET was peeled off. This is referred to as substrate A.

(4) Step of Roughening Treatment The insulating layer of the substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment:
Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd.) , an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C for 10 minutes, and finally a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous sulfuric acid solution). After being immersed at 40°C for 5 minutes, it was dried at 80°C for 15 minutes. This is referred to as roughened substrate A.

(5) Step of forming a conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the insulating layer of the roughened substrate A, a plating step (Atotech Japan Co., Ltd.) including the following steps 1 to 6 A copper plating process using a chemical solution manufactured by the company) was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
The surface of roughened substrate A was washed at 60° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
The surface of the roughened substrate A was treated with a sulfuric acid sodium peroxodisulfate aqueous solution at 30° C. for 1 minute.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
The surface of roughened substrate A was subjected to Pre. Dip Neoganth B (trade name) was used for 1 minute at room temperature.
4. Application of activator (application of Pd to the surface of the insulating layer)
The surface of roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35° C. for 5 minutes.
5. Reduction (reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A was treated with Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (trade name) and treated at 30° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
The surface of the roughened substrate A was mixed with Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). The solution was treated at 35° C. for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electroplating Process Next, an electrolytic copper plating process was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. under the condition that the via holes were filled with copper. After that, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm connected to the via hole and a circular conductor pattern with a diameter of 10 mm not connected to the lower layer conductor were used to form a 10 μm thick resist pattern on the surface of the insulating layer. Then, a conductor layer having lands and conductor patterns was formed. Annealing was then performed at 200° C. for 90 minutes. This board was designated as "evaluation board B".

<Measurement of thickness of insulating layer between conductor layers>
The cross-section of the evaluation substrate B was observed using an FIB-SEM composite device (“SMI3050SE” manufactured by SII Nano Technology Co., Ltd.). Specifically, a cross section perpendicular to the surface of the conductor layer was cut out by FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, cross-sectional SEM images were observed at five randomly selected locations, and the average value was defined as the thickness (μm) of the insulating layer between the conductor layers, and is shown in the table below.

<Evaluation of insulation reliability of insulating layer>
The circular conductor side with a diameter of 10 mm of the evaluation substrate B obtained above is used as a + electrode, and the lattice conductor (copper) side of the laminated plate connected to the land with a diameter of 1 mm is used as a - electrode. "PM422" manufactured by J-RAS Co., Ltd.), and the insulation resistance value after 200 hours under the conditions of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application was measured with an electrochemical migration tester (manufactured by J-RAS " ECM-100”). This measurement was performed 6 times, and if the resistance value of all 6 test pieces was 10 ⁷ Ω or more, it was evaluated as "○", and if even one of the test pieces was less than 10 ⁷ Ω, it was evaluated as "×". are shown in the table below together with the values. The insulation resistance values listed in the table below are the lowest insulation resistance values of the six test pieces.

The components used in the preparation of Resin Compositions 1 to 12 and their compounding amounts (in terms of non-volatile content) are shown in the table below.

In Examples 1 to 8, it has been confirmed that the same results as those of the above Examples can be obtained even if the components (D) to (G) are not contained, although there is a difference in degree.

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

Claims (16)

A resin composition containing (A) an epoxy resin, (B) a benzoxazine compound, and (C) an inorganic filler having an average particle size of 100 nm or less,
(B) component is represented by the following general formula (B-1),
A resin composition in which the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.

In formula (B-1), R ¹ is a group in which one or more arylene groups and one or more oxygen atoms are bonded, a group in which one or more alkylene groups and one or more oxygen atoms are bonded, and one or more arylene represents at least one n-valent group selected from the group consisting of groups in which a group, one or more alkylene groups, and one or more oxygen atoms are bonded, and each R ² is independently a halogen atom, an alkyl group, or an aryl group represents n represents an integer of 2-4 and m represents an integer of 0-4. (A) an epoxy resin, (B) a benzoxazine compound, (C) an inorganic filler having a specific surface area of 15 m ² /g or more (provided that silica that has been imidazole silane-treated and has an average particle size of 5 μm or less Except.) A resin composition containing
(B) component is represented by the following general formula (B-1),
A resin composition in which the content of component (C) is 40% by mass or more when the non-volatile component in the resin composition is taken as 100% by mass.

In formula (B-1), R ¹ is a group in which one or more arylene groups and one or more oxygen atoms are bonded, a group in which one or more alkylene groups and one or more oxygen atoms are bonded, and one or more arylene represents at least one n-valent group selected from the group consisting of groups in which a group, one or more alkylene groups, and one or more oxygen atoms are bonded, and each R ² is independently a halogen atom, an alkyl group, or an aryl group represents n represents an integer of 2-4 and m represents an integer of 0-4. 3. The resin composition according to claim 1, further comprising (D) a curing agent. 4. The resin composition according to claim 3, wherein the component (D) contains at least one of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. thing. The content of component (B) is 0.1% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of claims 1 to 4. Resin composition. 6. The invention according to any one of claims 1 to 5, wherein in general formula (B-1), R ¹ represents an n-valent group in which one or more arylene groups and one or more oxygen atoms are bonded. Resin composition. 7. The resin composition according to any one of claims 1 to 6, wherein the arylene group in R ¹ in general formula (B-1) is a phenylene group. The resin composition according to any one of claims 1 to 7, wherein m represents 0 in general formula (B-1). The resin composition according to any one of claims 1 to 8, which is used for forming an insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 9, which is used for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 10 provided on the support. 12. The resin sheet according to claim 11, wherein the resin composition layer has a thickness of 15 [mu]m or less. a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein the first conductor layer and the second conductor layer 13. The resin sheet according to claim 11 or 12, which is for forming the insulating layer of a printed wiring board having a distance of 6 μm or less. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 10. 15. The printed wiring board according to claim 14, wherein the distance between the first conductor layer and the second conductor layer is 6 [mu]m or less. A semiconductor device comprising the printed wiring board according to claim 14 or 15.

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