JP2022137095A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that yields an insulating layer having excellent embedding properties, low dielectric loss tangents, and excellent thermal expansion coefficients; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition.

SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound, (C) a polyamide-imide resin, and (D) an inorganic filler. The (D) inorganic filler has an average particle size of 100 nm or less, and/or the (D) inorganic filler has a specific surface of 15 m²/g or more.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,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.

As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. An 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

However, as in the resin composition described in Patent Document 1, when a large amount of inorganic filler is used, it may become difficult to control the lamination properties due to, for example, a decrease in embedding properties of the film due to an increase in melt viscosity. Are known. In particular, when the average particle size of the inorganic filler is small, the embedding property is remarkably lowered.

An object of the present invention is to provide a resin composition that provides an insulating layer that has good embeddability, a low dielectric loss tangent, and an excellent coefficient of thermal expansion; a resin sheet containing the resin composition; It is another object of the present invention to provide a printed wiring board and a semiconductor device each having an insulating layer.

Conventionally, resin compositions generally contain a thermoplastic resin such as a phenoxy resin, but the present inventors have found that the inclusion of a thermoplastic resin such as a phenoxy resin tends to increase the melt viscosity. I found that there is a tendency As a result of intensive studies by the present inventors to solve the above problems, the use of a polyamideimide resin suppresses the increase in melt viscosity and reduces the dielectric loss tangent even when a small-diameter inorganic filler is used. The present inventors have found that it is possible to achieve the present invention.

（式中、ｎは０～１５を表す。）
［８］ （Ｂ）成分の含有量が、樹脂成分１００質量％とした場合、１５質量％以上である、［１］～［７］のいずれかに記載の樹脂組成物。
［９］ プリント配線板の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］～［８］のいずれかに記載の樹脂組成物。
［１１］ 導体層を形成するため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。
［１２］ 支持体と、該支持体上に設けられた、［１］～［１１］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を含む、樹脂シート。
［１３］ 樹脂組成物層の厚みが１５μｍ以下である、［１２］に記載の樹脂シート。
［１４］ 樹脂組成物層中の残存溶剤量が、４質量％以下である、［１２］又は［１３］に記載の樹脂シート。
［１５］ 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］～［１１］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。
［１６］ ［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) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) A resin composition in which the inorganic filler has an average particle size of 100 nm or less.
[2] A resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) A resin composition in which the inorganic filler has a specific surface area of 15 m ² /g or more.
[3] The resin composition according to [1] or [2], wherein the content of component (C) is 3% by mass or more and 30% by mass or less when the resin component is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein the content of component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. .
[5] The resin composition according to any one of [1] to [4], wherein component (C) has an isocyanuric ring structure.
[6] The resin composition according to any one of [1] to [5], wherein component (C) has a repeating unit containing an isocyanuric ring structure and an alicyclic structure.
[7] The resin composition according to any one of [1] to [6], wherein component (C) is represented by the following general formula (I).

(In the formula, n represents 0 to 15.)
[8] The resin composition according to any one of [1] to [7], wherein the content of component (B) is 15% by mass or more based on 100% by mass of the resin component.
[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 [8], which is used for forming an interlayer insulating layer of a printed wiring board.
[11] The resin composition according to any one of [1] to [8], which is used for forming an insulating layer for forming a conductor layer.
[12] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [11].
[13] The resin sheet of [12], wherein the resin composition layer has a thickness of 15 μm or less.
[14] The resin sheet according to [12] or [13], wherein the amount of residual solvent in the resin composition layer is 4% by mass or less.
[15] 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 [11].
[16] A semiconductor device including the printed wiring board according to [15].

According to the present invention, a resin composition that provides an insulating layer with good embeddability, low dielectric loss tangent, and excellent thermal expansion coefficient; a resin sheet containing the resin composition; Thus, a printed wiring board 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 resin composition of the first embodiment of the present invention is a resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler, (D) The inorganic filler has an average particle size of 100 nm or less. Further, the resin composition of the second embodiment of the present invention is a resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler. and (D) the inorganic filler has a specific surface area of 15 m ² /g or more. With the resin compositions of the first and second embodiments, it is possible to provide a resin composition that provides an insulating layer with good embeddability, low dielectric loss tangent, and excellent coefficient of thermal expansion.

The term “resin component” refers to non-volatile components constituting the resin composition, excluding (D) an inorganic filler described later. Each component contained in the first and second resin compositions will be described in detail below. Here, the first resin composition and the second resin composition 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, bisphenol AF type epoxy resins and fluorine-containing epoxy resins such as perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolak type epoxy resin; phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; Epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Resins; spiro ring-containing epoxy resins; cyclohexanedimethanol-type epoxy resins; naphthylene ether-type epoxy resins; trimethylol-type epoxy resins; An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy resin preferably contains an epoxy resin having 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. The epoxy resin has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and/or three or more epoxy groups in one molecule. and is solid at a temperature of 20° C. (hereinafter referred to as “solid epoxy resin”). As the epoxy resin, a liquid epoxy resin and a solid epoxy resin may be used in combination.

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. An alicyclic epoxy resin having a type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation, and "828US" and "jER828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation. , "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin) , Daicel's "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel & Sumikin Chemical Co., Ltd.'s "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), Daikin Industries Ltd.'s "E-7432", "E-7632" (perfluoroalkyl type epoxy resin), etc. mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are 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", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311 ”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (naphthylene ether type epoxy resin), “EPPN-502H” manufactured by Nippon 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 novolak type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "jER1010", ( solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and the like.

When a liquid epoxy resin and a solid epoxy resin are used together as epoxy resins, the ratio by mass (liquid epoxy resin:solid epoxy resin) is in the range of 1:0.1 to 1:15. A range of 1:0.1 to 1:10 is preferred, and a range of 1:0.3 to 1:3 is even more preferred.

From the viewpoint of obtaining an insulating layer exhibiting good tensile breaking strength and insulation reliability, the content of the epoxy resin in the resin composition is preferably 10% by mass or more, more preferably 10% by mass, when the resin component is 100% by mass. It is 25% by mass or more, more preferably 45% by 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 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition layer 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 the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. 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) Active ester compound>
The resin composition contains (B) an active ester compound. An active ester compound is an active ester compound having one or more active ester groups in one molecule. The active ester compound is preferably an active ester compound having two or more active ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like. An active ester compound having two or more highly reactive ester groups in one molecule is preferably used. An active ester compound may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of improving heat resistance, an active ester compound 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 is preferred. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group. Obtained by reacting, more preferably an aromatic compound having two or more active ester groups in one molecule, a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group An aromatic compound obtained by reacting with an aromatic compound and having two or more active ester groups in one molecule is even more preferable. The active ester compound may be linear or branched. Also, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, Heat resistance can be increased.

Examples of carboxylic acid compounds include aliphatic carboxylic acids having 1 to 20 carbon atoms and aromatic carboxylic acids having 7 to 20 carbon atoms. The aliphatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 8 carbon atoms, specifically acetic acid, malonic acid, succinic acid, and malein. acid, itaconic acid, and the like. The aromatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, and specifically includes benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. . Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred, from the viewpoint of heat resistance.

The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

The phenol compound preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 23 carbon atoms, and even more preferably 6 to 22 carbon atoms. Preferred specific examples of phenol 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol and the like. As the phenol compound, a phenol novolak and a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may also be used.

The naphthol compound preferably has, for example, 10 to 40 carbon atoms, more preferably 10 to 30 carbon atoms, and even more preferably 10 to 20 carbon atoms. Preferred specific examples of naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. Naphthol novolacs may also be used as naphthol compounds.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, phosphorus atom-containing oligomers having phenolic hydroxyl groups are preferred, catechol, 1,5 -dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, phosphorus having a phenolic hydroxyl group Atom-containing oligomers are more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, phenol Further preferred are phosphorus atom-containing oligomers having a hydroxy group, such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolak, and phosphorus atoms having a phenolic hydroxyl group. Oligomers containing dicyclo Pentadiene-type diphenols are particularly preferred.

The thiol compound is not particularly limited, and examples thereof include benzenedithiol, triazinedithiol, and the like.

Preferred specific examples of the active ester compound include 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 phenol novolac, and a benzoylated phenol novolak. Examples include active ester compounds and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Active ester compounds and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable. In the present invention, the "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As the active ester compound, active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, and commercially available active ester compounds may also be used. Commercially available active ester compounds include, for example, DIC's "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" (dicyclopentadiene type diphenol structure Active ester compound containing), DIC "EXB9416-70BK" (active ester compound containing naphthalene structure), Mitsubishi Chemical Corporation "DC808" (active ester compound containing phenol novolac acetylated product), Mitsubishi Chemical Corporation "YLH1026" (an active ester compound containing a benzoylated phenol novolak) manufactured by DIC Corporation, and "EXB9050L-62M" (an active ester compound containing a phosphorus atom) manufactured by DIC Corporation.

From the viewpoint of lowering the dielectric loss tangent, the content of the active ester compound in the resin composition is preferably 15% by mass or more, more preferably 17% by mass or more, and 20% by mass or more when the resin component is 100% by mass. is more preferred. Although the upper limit of the content of the active ester compound is not particularly limited, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

Further, when the number of epoxy groups of (A) epoxy resin is 1, the number of reactive groups of (B) active ester compound is preferably 0.1 to 2, and 0.2, from the viewpoint of obtaining an insulating layer with good mechanical strength. ~1.5 is more preferred, and 0.3 to 1 is even more preferred. Here, the "epoxy group number of the epoxy resin" is the sum of the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all the epoxy resins. In addition, "reactive group" means a functional group capable of reacting with an epoxy group, and "the number of reactive groups of the active ester compound" refers to the solid content mass of the active ester compound present in the resin composition. It is the sum of all the values divided by the reactive group equivalent.

<(C) Polyamideimide resin>
The resin composition contains (C) a polyamide-imide resin. As described above, conventionally, resin compositions generally contain a thermoplastic resin such as a phenoxy resin. It was found that the viscosity increased. In the present invention, by using (C) the polyamide-imide resin, it is possible to suppress an increase in melt viscosity and to decrease the dielectric loss tangent and the coefficient of linear thermal expansion (CTE). (C) Polyamideimide resins have a lower polarity than thermoplastic resins such as phenoxy resins. In addition, polyamide-imide resins are less likely to produce highly polar components such as alcohol during curing. Therefore, it is considered that the dielectric loss tangent can be reduced. In addition, since the imide skeleton in the (C) polyamide-imide resin has a rigid structure, it is difficult to expand, so it is thought that the coefficient of linear thermal expansion decreases. Furthermore, due to the action of the amide skeleton and the imide skeleton, the polyamide-imide resin exhibits high compatibility with the active ester compound, so it is thought that an increase in melt viscosity can be suppressed.

(C) polyamideimide resin, from the viewpoint of compatibility with other components in the resin composition, polyamideimide resin having an alicyclic structure in the molecular structure, the siloxane structure described in JP-A-05-112760 , a polyamideimide resin having a bulky branched chain structure, a polyamideimide resin using an asymmetric monomer as a raw material, a polyamideimide resin having a multi-branched structure, and the like are preferably used.

Among them, the isocyanuric ring structure improves the compatibility with (B) the active ester compound, and the network structure of the branched isocyanuric ring structure improves the compatibility and dispersibility of the resin varnish. From, (i) a polyamideimide resin having an isocyanuric ring structure in the molecular structure (that is, a polyamideimide resin having an isocyanuric ring structure and an imide skeleton or an amide skeleton) (ii) an isocyanuric ring structure and an alicyclic Polyamideimide resin having a structure (that is, a polyamideimide resin having an isocyanuric ring structure, an alicyclic structure, an imide skeleton or an amide skeleton), (iii) having a repeating unit containing an isocyanuric ring structure and an alicyclic structure A polyamideimide resin (that is, a polyamideimide resin having a repeating unit containing an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton) is more preferred, and the polyamideimide resin of (iii) is even more preferred.

As a preferred embodiment of the polyamideimide resins (i) to (iii), (1) an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic structure diisocyanate and a polycarboxylic acid having 3 or more carboxyl groups Carboxylic acid group-containing branched polyamideimide (hereinafter, the compound may be referred to as "(compound C-1)".), (2) compound (C- 1) a carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter referred to as "compound (C-2 )”), or (3) reacting the residual isocyanate group with a compound having one hydroxyl group and one or more radically polymerizable unsaturated groups in the process of synthesizing the compound (C-1). Examples thereof include a carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter sometimes referred to as "compound (C-3)"), which is the resulting compound.

（式中、ｎは０～１５を表す。） Specific examples of the compound (C-1) include compounds represented by the following general formula (I). The repeating unit in the compound represented by formula (I) is referred to as repeating unit (I-1).

(In the formula, n represents 0 to 15.)

（式中、Ｒは式（Ｉ）中の残基を表す。） As the compound (C-2), a structure (I- 2) is exemplified by compound (II).

(Wherein R represents a residue in formula (I).)

The ratio of GMA modification of the carboxyl group is preferably 0.3 mol% or more, more preferably 0.5 mol% or more, still more preferably 0.5 mol% or more, with respect to the number of moles of carboxyl groups of the compound (C-1), in which GMA is added. It is 0.7 mol % or more, or 0.9 mol % or more. The upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, or 20 mol% or less.

（式中、Ｒ’は式（Ｉ）中の残基を表す。） As the compound (C-3), any part of the repeating unit (I-1) in the above formula (I) and/or the terminal imide group is an isocyanate residue, to which the hydroxyl group of pentaerythritol triacrylate is added. Compound (III) having the structure (I-3) represented by

(Wherein, R' represents a residue in formula (I).)

The upper limit of the amount of pentaerythritol triacrylate added is preferably 40 mol %, more preferably 38 mol %, and still more preferably 35 mol %, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of preparation. On the other hand, the lower limit of the amount of pentaerythritol triacrylate to be added is preferably 0.3 mol%, or 3 mol, relative to the number of moles of isocyanate groups in the polyisocyanate at the time of charging, from the viewpoint of sufficiently obtaining the effect of addition. % is more preferred, and 5 mol % is even more preferred.

Polyamideimide resins can be synthesized by various known methods. As a method for synthesizing a polyamideimide resin, for example, paragraphs 0020 to 0030 of International Publication No. WO 2010/074197 can be referred to, the contents of which are incorporated herein.

A commercially available polyamide-imide resin can also be used as the polyamide-imide resin. Examples of commercially available polyamideimide resins include "V-8000" and "ELG503" manufactured by DIC. For example, compound (II) can be obtained by reacting glycidyl methacrylate with "V-8000" manufactured by DIC.

The content of the polyamideimide resin in the resin composition is preferably 1% by mass or more when the resin component is 100% by mass, from the viewpoint of providing an insulating layer having a low melt viscosity and a low dielectric loss tangent and a low coefficient of thermal expansion. 2% by mass or more is more preferable, and 3% by mass or more is even more preferable. Although the upper limit is not particularly limited, it is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less.

<(D) Inorganic filler>
The resin composition of the first embodiment contains (D) an inorganic filler, and the average particle size of the (D) inorganic filler is 100 nm or less. Further, the resin composition of the second embodiment contains (D) an inorganic filler, and the (D) inorganic filler has a specific surface area of 15 m ² /g or more.

The material of the inorganic filler is not particularly limited as long as it is an inorganic compound. Examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotal. Site, 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, magnesium titanate, titanium Examples include bismuth oxide, 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 size of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably 90 nm or less, from the viewpoint of increasing the specific surface area of the inorganic filler and decreasing the dielectric loss tangent and the linear thermal expansion coefficient. is 80 nm or less. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 70 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, from the viewpoint of increasing the specific surface area of the inorganic filler and decreasing the dielectric loss tangent and the linear thermal expansion coefficient. , and more preferably 80 nm or less. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 50 nm or more, more preferably 60 nm or more, and still more preferably 70 nm or more.
Examples of commercially available inorganic fillers having such an average particle size include "UFP-30" and "UFP-40" manufactured by Denki Kagaku Kogyo.

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 is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As a measurement sample, one obtained by dispersing an inorganic filler in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, Horiba's "LA-500", Shimadzu Corporation's "SALD-2200" and the like can be used.

The specific surface area of the inorganic filler in the second embodiment is 15 m ² /g or more, preferably 20 m ² /g or more, more preferably 30 m ² /g or more, from the viewpoint of reducing dielectric loss tangent and linear thermal expansion coefficient. is. 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 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, from the viewpoint of reducing dielectric loss tangent and linear thermal expansion coefficient. That's it. 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.

Inorganic fillers include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and alkoxysilanes, from the viewpoint of improving moisture resistance and dispersibility. , an organosilazane compound, and a titanate-based coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu 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).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is 0.2 parts by mass to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the inorganic filler. preferably 0.2 to 3 parts by mass, more preferably 0.3 to 2 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. 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, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above 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 inorganic filler can be measured after the surface-treated 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 inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of lowering the dielectric loss tangent, the content of the inorganic filler is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass when the non-volatile component in the resin composition is 100% by mass. % by mass or more, 45% by mass or more, or 50% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, or 75% by mass, from the viewpoint of the mechanical strength of the insulating layer. % or less.

<(E) flame retardant>
In one embodiment, the resin composition may contain (E) a flame retardant. Examples of flame retardants include 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 a flame retardant, the content of the flame retardant is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more when the resin component is 100% by mass. is. The upper limit is preferably 6% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less.

<(F) Curing agent (excluding component (B))>
In one embodiment, the resin composition may contain (F) a curing agent. However, the curing agent here does not include (B) an active ester compound. (F) The curing agent is not particularly limited as long as it has a function of curing (A) the epoxy resin. Examples include carbodiimide curing agents. A single curing agent may be used alone, or two or more curing agents may be used in combination. Component (F) is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, and cyanate ester-based curing agents.

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", Nippon Steel & Sumikin "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395", DIC's "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

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

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.

When the resin composition contains (F) a curing agent, the amount ratio of (A) epoxy resin and (F) curing agent is [total number of epoxy groups in (A) epoxy resin]:[(F) curing total number of reactive groups of the agent] is preferably in the range of 1:0.01 to 1:3, more preferably 1:0.015 to 1:2, and 1:0.02 to 1:1.5. is more preferred. Here, the reactive group of the (F) curing agent is an active hydroxyl group or the like, and differs depending on the type of the (F) curing agent. The total number of reactive groups in the (F) curing agent is the sum of the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all the (F) curing agents.

Further, when the resin composition contains (F) a curing agent, the amount ratio of (A) the epoxy resin, (B) the active ester compound and (F) the curing agent is [(A) the epoxy group of the epoxy resin ]:[total number of reactive groups of (B) the active ester compound and (F) the reactive groups of the curing agent] is preferably in the range of 1:0.01 to 1:3, and 1:0. 015 to 1:2 is more preferred, and 1:0.02 to 1:1.5 is even more preferred.

When the resin composition contains (F) a curing agent, the content of (F) the curing agent is preferably 30% by mass or less, more preferably 25% by mass or less, when the resin component is 100% by mass. Preferably, it is 20% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more.

<(G) Curing accelerator>
In one embodiment, the resin composition may contain (G) 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 imidazole-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, and examples thereof include "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 to 1% by mass, and 0.01% by mass to 0.01% by mass, when the resin component is 100% by mass. 5 mass % is more preferable, and 0.01 mass % to 0.3 mass % is even more preferable.

<(H) Thermoplastic resin>
In one embodiment, the resin composition may contain (H) a thermoplastic resin within a range that does not impair the effects of the present invention. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, A polyester resin is mentioned. The thermoplastic resin may be used singly or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 40,000 or more. Although the upper limit is not particularly limited, it is preferably 70,000 or less, more preferably 60,000 or less. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K- manufactured by Showa Denko Co., Ltd. as a column. 804L can be measured at a column temperature of 40° C. using chloroform or the like as a mobile phase, and can be calculated 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 the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include vinyl group-containing oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.

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

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 1 to 10% by mass, and 1.5 to 5% by mass, when the nonvolatile component in the resin composition is 100% by mass. is more preferable, and 2% by mass to 5% by mass is even more preferable.

<(I) 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.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1 to 20% by mass, and 0.2 to 10% by mass when the non-volatile component in the resin composition is 100% by mass. % by mass is more preferred, and 0.3 to 5% by mass, or even more preferably 0.5 to 3% by mass.

<Physical properties and applications of the resin composition>
INDUSTRIAL APPLICABILITY The resin composition of the present invention can provide an insulating layer having good embedding properties, a low dielectric loss tangent, and an excellent coefficient of thermal expansion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer contained in an electronic component. It can be suitably used as a (resin composition for insulating layer of printed wiring board), and as a resin composition for forming an interlayer insulating layer of printed wiring board (resin composition for interlayer insulating layer of printed wiring board) It can be used more preferably. 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.

The resin composition of the present invention can also be suitably used as a resin composition for forming a conductor layer (an insulating layer-forming resin composition for forming a conductor layer). Furthermore, a resin composition for encapsulating an electronic member can also be suitably used. It can be used preferably.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. That is, it results in an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.009 or less, still more preferably 0.008 or less, and even more preferably 0.0076 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric loss tangent and coefficient of linear thermal expansion (CTE)> described later.

A cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits a characteristic of a low coefficient of linear thermal expansion (CTE). That is, it results in an insulating layer with a low coefficient of linear thermal expansion. The coefficient of linear thermal expansion is preferably 35 ppm or less, more preferably 33 ppm or less, and even more preferably 30 ppm or less. Although the lower limit is not particularly limited, it may be 1 ppm or more. The coefficient of linear thermal expansion (CTE) can be measured according to the method described in <Measurement of Dielectric Loss Tangent and Coefficient of Linear Thermal Expansion (CTE)> below.

The melt viscosity of the resin composition at 120° C. is preferably 6000 poise or less, more preferably 5000 poise or less, still more preferably 4000 poise or less, from the viewpoint of suppressing cracks and circuit distortion. The lower limit of the melt viscosity is preferably 100 poise or more, more preferably 1000 poise or more, from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. The melt viscosity can be measured by a dynamic viscoelasticity method, for example, according to the method described in <Measurement of Melt Viscosity> below.

[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 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 20 μm or less, 15 μm or less, or 10 μm or less, from the viewpoint of thinning the printed wiring board. be. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 3 μm or more, or the like.

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.

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

From the viewpoint of improving thickness stability during thin film formation, the ratio of the content of the resin varnish to the solid content in the resin varnish (solid content/resin varnish content) is preferably It is 0.5 or more, more preferably 0.55 or more, and still more preferably 0.6 or more. Although the upper limit is not particularly limited, it is preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.7 or less.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone, and acetic esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. , carbitols such as cellosolve and butyl carbitol, 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. Although the drying conditions are not particularly limited, the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 4% 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.

In the resin sheet, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). 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, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. 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 composition layer exhibits the characteristic that the melt viscosity can be lowered even when the amount of residual solvent is small. Therefore, an insulating layer with good embedding properties can be obtained. The amount of residual solvent in the resin composition layer is preferably 4% or less, more preferably 3.8% or less, and even more preferably 3.7% or less. Although the lower limit is not particularly limited, it may be 0.1% or more. The amount of residual solvent can be measured according to the method described in <Measurement of amount of residual solvent> described later.

In addition, since the resin composition layer contains a polyamide-imide resin, even if it contains an inorganic filler having an average particle size of 100 nm or less, it exhibits excellent embedding properties and suppresses the generation of voids. For example, among the 255 × 340 mm size substrates produced using the resin composition layer in the present invention, even if three arbitrarily set 1 cm squares on the wiring pattern are observed, appearance defects with a diameter of 10 μm or more ( voids) do not exist. The presence or absence of voids can be measured by the method described later in <Evaluation of presence or absence of voids>.

[Printed wiring board, method for manufacturing 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).

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. Although the lower limit is not particularly limited, it can 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, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120° C. to 240° C. (preferably in the range of 150° C. to 220° C., more preferably in the range of 170° C. to 200° C. range) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before 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 more and less than 120° C. (preferably 60° C. or more and 110° C. or less, more preferably 70° C. or more and 100° C. or less). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 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 the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive 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 "%" mean "mass parts" and "mass%", respectively, unless otherwise specified.

<Example 1: Preparation of resin composition 1>
Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation "828US", epoxy equivalent of about 180) 8 parts, biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent of about 190) 15 parts, and naphthol type epoxy resin (Nippon Steel 15 parts of "ESN475V" manufactured by Sumikin Chemical Co., Ltd., epoxy equivalent of about 330) and 3 parts of phosphazene resin ("SPH-100" manufactured by Otsuka Chemical Co., Ltd.) were heated and dissolved in 50 parts of methyl ethyl ketone (MEK) with stirring. After cooling to room temperature, hyperbranched polyamideimide resin (manufactured by DIC "ELG503", n-butyl acetate solution with a solid content of 50% by mass) 6 parts, active ester compound (manufactured by DIC "HPC-8000-65T" , active group equivalent of about 223, solid content of 65 mass% toluene solution) 30 parts, phenolic curing agent (DIC Corporation "LA-3018-50P", active group equivalent of about 151, solid content of 50% 2-methoxypropanol solution) 10 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 3 parts, spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm , and a specific surface area of 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) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2>
In the preparation of resin composition 1, 30 parts of an active ester compound ("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 compound (manufactured by DIC "EXB9416-70BK", an active group equivalent of about 274, a methyl isobutyl ketone (MIBK) solution with a solid content of 70 mass%) was changed to 30 parts. A resin composition 2 was prepared in the same manner as the resin composition 1 except for the above items.

<Example 3: Preparation of resin composition 3>
In the preparation of resin composition 1, 6 parts of a hyperbranched polyamideimide resin (“ELG503” manufactured by DIC, n-butyl acetate solution with a solid content of 50% by mass) was added to 6 parts of a hyperbranched polyamideimide resin (“V -8000 BM", a 3:1 solution of n-butyl acetate and MEK with a solid content of 45% by mass)) was changed to 6 parts. A resin composition 3 was prepared in the same manner as the resin composition 1 except for the above matters.

<Example 4: Preparation of resin composition 4>
In the preparation of resin composition 1, 6 parts of a hyperbranched polyamideimide resin ("ELG503" manufactured by DIC Corporation, n-butyl acetate solution with a solid content of 50% by mass) was added to 6 parts of the hyperbranched polyamideimide resin (manufactured by DIC Corporation "ELG503", n-butyl acetate solution with a solid content of 50 mass%) was changed to 15 parts. A resin composition 4 was prepared in the same manner as the resin composition 1 except for the above matters.

<Example 5: Preparation of resin composition 5>
In the preparation of resin composition 1, 12 parts of a carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution having an active group equivalent of about 216 and a solid content of 50% by mass) was added before adding the curing accelerator. A resin composition 5 was prepared in the same manner as the resin composition 1 except for the above items.

<Example 6: Preparation of resin composition 6>
In the production of resin composition 1, the amount of methyl ethyl ketone (MEK) was changed to 60 parts, and the amount of spherical silica was changed to 90 parts. A resin composition 6 was prepared in the same manner as the resin composition 1 except for the above items.

<Example 7: Preparation of resin composition 7>
In the preparation of resin composition 6, 30 parts of an active ester compound ("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 compound (manufactured by DIC "EXB9416-70BK", an MIBK solution with an active group equivalent of about 274 and a solid content of 70% by mass) was changed to 30 parts. A resin composition 7 was prepared in the same manner as the resin composition 1 except for the above items.

<Comparative Example 1: Production of resin composition 8>
In the preparation of resin composition 1, 6 parts of a hyperbranched polyamideimide resin (“ELG503” manufactured by DIC Corporation, n-butyl acetate solution with a solid content of 50% by mass) was added to 6 parts of a phenoxy resin (“YL7553BH30” manufactured by Mitsubishi Chemical Corporation, solid 10 parts of a 1:1 solution of 30% by mass of MEK and cyclohexanone). A resin composition 8 was prepared in the same manner as the resin composition 1 except for the above items.

<Comparative Example 2: Production of resin composition 9>
In the preparation of resin composition 8”, 30 parts of an active ester compound (manufactured by DIC “HPC-8000-65T”, an active group equivalent of about 223, a toluene solution with a solid content of 65% by mass) was added to an active ester compound (manufactured by DIC "EXB9416-70BK", an MIBK solution with an active group equivalent of about 274 and a solid content of 70% by mass) was changed to 30 parts. A resin composition 9 was prepared in the same manner as the resin composition 8 except for the above items.

<Comparative Example 3: Production of resin composition 10>
In the production of resin composition 8, the amount of MEK was changed to 60 parts, and the amount of spherical silica was changed to 90 parts. A resin composition 10 was prepared in the same manner as the resin composition 8 except for the above items.

<Comparative Example 4: Production of resin composition 11>
In the preparation of resin composition 8, 10 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was added to 10 parts of a phenoxy resin ("YL6954BH30" manufactured by Mitsubishi Chemical Corporation, solid 10 parts of a 1:1 solution of 30% by mass of MEK and cyclohexanone). A resin composition 11 was prepared in the same manner as the resin composition 8 except for the above matters.

<Comparative Example 5: Production of resin composition 12>
In the preparation of resin composition 8, 10 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) was added to an ester-type phenoxy resin ("YL7891BH30" manufactured by Mitsubishi Chemical Corporation). , a 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass)) was changed to 10 parts. A resin composition 12 was prepared in the same manner as the resin composition 8 except for the above matters.

<Comparative Example 6: Production of resin composition 13>
In the preparation of resin composition 8, 30 parts of an active ester compound ("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 compound (manufactured by DIC "EXB9416-70BK", an MIBK solution with an active group equivalent of about 274 and a solid content of 70% by mass) was changed to 30 parts. A resin composition 13 was prepared in the same manner as the resin composition 8 except for the above items.

<Production of resin sheet>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C., “release PET”) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec). prepared.

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 7.5 μm, and dried at 70 ° C. to 95 ° C. for 2 minutes. A resin composition layer was obtained on the release PET. Next, on the surface of the resin sheet that is not bonded to the support, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is attached to the resin composition layer. laminated to. As a result, a resin sheet A was produced, which consisted of the release PET (support), the resin composition layer, and the protective film in that order.

In addition, resin sheet B was formed in the same manner as resin sheet A, except that the resin composition layer after drying was uniformly coated with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 75° C. to 100° C. for 4 minutes. made.

<Evaluation of presence or absence of voids>
(1) Surface treatment of inner layer circuit board As an inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper) having circuit conductors (copper) formed with a wiring pattern of L/S = 2 µm/2 µm on both sides ( A copper foil with a thickness of 3 μm, a substrate with a thickness of 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size of 255×340 mm was prepared.

(2) Lamination of resin sheets The protective film is peeled off from each resin sheet A 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 inner layer circuit board so that the inner layer circuit board was in contact with the inner layer circuit board. Lamination was carried out by pressure bonding for 45 seconds at 100° C. and a pressure of 0.74 MPa after reducing the pressure for 30 seconds to an air pressure of 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board laminated with the resin sheet A is placed in an oven at 100°C for 30 minutes, then transferred to an oven at 180°C for 30 minutes, then heat-cured and insulated. A void evaluation substrate was produced by forming a layer and peeling off the release PET.

(4) Evaluation of the presence or absence of voids Using Hilox's "DIGITAL MICROSCOPE KH-8700", arbitrarily set 1 cm squares on the wiring pattern of the board for void evaluation were observed at three points. A case in which one or more voids, which are defects in the appearance described above, was present was evaluated as "x", and a case in which there were no voids was evaluated as "good". The absence of voids indicates excellent embeddability.

<Measurement of dielectric loss tangent and coefficient of linear thermal expansion (CTE)>
Each resin sheet B prepared in advance was thermally cured at 200° C. for 90 minutes, and then the release PET was peeled off to prepare a cured physical property evaluation sample.

(Measurement of dielectric loss tangent)
A sample for evaluation of cured physical properties was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated.

(Measurement of coefficient of linear thermal expansion (CTE))
The sample for evaluation of cured physical properties was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile loading method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. An average linear thermal expansion coefficient (ppm) from 25° C. to 80° C. in the second measurement was calculated.

<Measurement of melt viscosity>
The melt viscosity of the resin composition layer of each resin sheet A prepared in advance was measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from the starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, and the measurement temperature interval was 2.5 ° C., vibration 1 Hz, strain The dynamic viscoelastic modulus was measured under the measurement conditions of 5 deg, and the melt viscosity at 120°C was measured.

<Measurement of residual solvent amount>
First, each resin sheet A prepared in advance was cut into 10 cm squares, and the mass thereof was measured (this measured mass is referred to as "A"). Next, the resin sheet A cut into 10 cm squares was dried at 130° C. for 15 minutes, and the mass was measured again (this measured mass is referred to as “B”). Finally, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) that has been subjected to release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec) used as a support is 10 cm long. A corner was cut out and its mass was measured (this measured mass is referred to as "C"). The amount of residual solvent was obtained by applying the measured masses A to C to the following formula 1.
Residual solvent amount = (A - B) / (A - C) x 100 (Formula 1)

The average particle size and specific surface area of the inorganic fillers used in Resin Compositions 1 to 13 were measured as follows.

<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 from the median diameter.

<Measurement of specific surface area of inorganic filler>
Using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co.), nitrogen gas is adsorbed on the sample surface, and the specific surface area is calculated using the BET multipoint method to determine the specific surface area of the inorganic filler. was measured.

The following table shows the components used in the preparation of Resin Compositions 1 to 13, their compounding amounts (mass parts), the presence or absence of voids, the melt viscosity, the amount of residual solvent, the dielectric loss tangent, and the CTE. Abbreviations and the like in the table below are as follows.
828US: Bisphenol A type epoxy resin, epoxy equivalent of about 180, manufactured by Mitsubishi Chemical Corporation ESN475V: Naphthol type epoxy resin, epoxy equivalent of about 330, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. YX4000HK: Biphenyl type epoxy resin, epoxy equivalent of about 190, manufactured by Mitsubishi Chemical Corporation HPC-8000-65T: active ester compound, active group equivalent of about 223, manufactured by DIC EXB-9416-70BK: active ester compound, active group equivalent of about 274, manufactured by DIC ELG503: polyamideimide resin, V-8000BM manufactured by DIC : Polyamideimide resin, UFP-30 manufactured by DIC Corporation: Spherical silica, average particle size 0.078 μm, SPH-100 manufactured by Denki Kagaku Kogyo Co., Ltd.: Phosphazene resin, LA-3018-50P manufactured by Otsuka Chemical Co., Ltd.: Phenolic curing agent, activity Base equivalent of about 151, V-03 manufactured by DIC: carbodiimide compound, active group equivalent of about 216, DMAP manufactured by Nisshinbo Chemical Co., Ltd.: curing accelerator, 4-dimethylaminopyridine YL7553BH30: phenoxy resin, YL6954BH30 manufactured by Mitsubishi Chemical Corporation: phenoxy resin, YL7891BH30 manufactured by Mitsubishi Chemical Corporation: phenoxy resin, manufactured by Mitsubishi Chemical Corporation

In Examples 1 to 7, even if the components (E) to (G) are not contained, it has been confirmed that the same results as in the above examples are obtained 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 (14)

(A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) a resin composition containing an inorganic filler,
The content of the component (B) is 15% by mass or more and 50% by mass or less when the resin component is 100% by mass,
(C) component has either an isocyanuric ring structure or an alicyclic structure,
(C) The content of the component is 3% by mass or more and 30% by mass or less when the resin component is 100% by mass,
(D) A resin composition in which the inorganic filler has an average particle size of 100 nm or less. (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) a resin composition containing an inorganic filler,
The content of the component (B) is 15% by mass or more and 50% by mass or less when the resin component is 100% by mass,
(C) component has either an isocyanuric ring structure or an alicyclic structure,
(C) The content of the component is 3% by mass or more and 30% by mass or less when the resin component is 100% by mass,
(D) A resin composition in which the inorganic filler has a specific surface area of 15 m ² /g or more. 3. The resin composition according to claim 1, wherein the content of component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein component (C) has an isocyanuric ring structure. 5. The resin composition according to any one of claims 1 to 4, wherein component (C) has a repeating unit containing an isocyanuric ring structure and an alicyclic structure. The resin composition according to any one of claims 1 to 5, wherein component (C) is represented by the following general formula (I).

(In the formula, n represents 0 to 15.) The resin composition according to any one of claims 1 to 6, which is used for forming an insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer for forming a conductor layer. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 9 provided on the support. 11. The resin sheet according to claim 10, wherein the resin composition layer has a thickness of 15 [mu]m or less. The resin sheet according to claim 10 or 11, wherein the amount of residual solvent in the resin composition layer is 4% by mass 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 9. A semiconductor device comprising the printed wiring board according to claim 13 .

Images