JP2018131619A - Resin composition - Google Patents

Abstract

A resin composition that provides an insulating layer with good embeddability, a low dielectric loss tangent, and an excellent thermal expansion coefficient; a resin sheet containing the resin composition; an insulating layer formed using the resin composition A printed wiring board provided with a semiconductor device and a semiconductor device. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler, wherein (D) the average particle diameter of the inorganic filler Is a resin composition in which the specific surface area of the inorganic filler is 15 m 2 / g or more. [Selection figure] None

Description

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

  As a printed wiring board manufacturing technique, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 includes an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin, and an inorganic filler, and the content of the inorganic filler is 100% by mass of the non-volatile component in the resin composition. The resin composition which is 40 mass% or more is described.

JP 2016-27097 A

  However, when a large amount of inorganic filler is used as in the resin composition described in Patent Document 1, it may be difficult to control the laminating property due to a decrease in embedding property of the film due to an increase in melt viscosity. Are known. In particular, when the average particle diameter of the inorganic filler is small, the embeddability is significantly reduced.

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

  Conventionally, a resin composition generally contains a thermoplastic resin such as a phenoxy resin, but the present inventors tend to increase the melt viscosity when a thermoplastic resin such as a phenoxy resin is contained. Found that there is a tendency to become. As a result of intensive studies to solve the above problems, the present inventors have suppressed the increase in melt viscosity and reduced the dielectric loss tangent even when using a small-diameter inorganic filler by using a polyamideimide resin. As a result, the present invention has been completed.

（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 comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) The resin composition whose average particle diameter of an inorganic filler is 100 nm or less.
[2] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) The resin composition whose specific surface area of an inorganic filler is 15 m < ² > / g or more.
[3] The resin composition according to [1] or [2], wherein the content of the 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 the component (D) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. .
[5] The resin composition according to any one of [1] to [4], wherein the component (C) has an isocyanuric ring structure.
[6] The resin composition according to any one of [1] to [5], wherein the 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 the component (C) is represented by the following general formula (I).

(In the formula, n represents 0-15.)
[8] The resin composition according to any one of [1] to [7], wherein the content of the component (B) is 15% by mass or more when the resin component is 100% by mass.
[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer of a printed wiring board.
[10] The resin composition according to any one of [1] to [8], which is 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 for forming an insulating layer for forming a conductor layer.
[12] A resin sheet comprising a support and a resin composition layer formed on the support and formed from the resin composition according to any one of [1] to [11].
[13] The resin sheet according to [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 including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [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 embedding properties, low dielectric loss tangent, and excellent thermal expansion coefficient; a resin sheet containing the resin composition; and formed using the resin composition. A printed wiring board provided with an insulating layer 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 comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler, (D) The average particle size of the inorganic filler is 100 nm or less. 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. (D) The specific surface area of the inorganic filler is 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 embedding properties, low dielectric loss tangent, and excellent thermal expansion coefficient.

  The “resin component” refers to a component excluding the inorganic filler (D) described later among the non-volatile components constituting the resin composition. Hereinafter, each component contained in the first and second resin compositions will be described in detail. 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. Examples of (A) epoxy resins include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and 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 novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; Epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Epoxy resin having butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane dimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; Examples include ethane 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 nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin has two or more epoxy groups in one molecule and is a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and / or three or more epoxy groups in one molecule. It is preferably a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. As the epoxy resin, a liquid epoxy resin and a solid epoxy resin may be used in combination.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 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” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation , Daicel "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Glycidylcyclohexane), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “E-7432”, “E-7632” (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd., and the like. These may be used alone or in combination of two or more.

  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 preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "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 novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG” manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation," jER1010 "manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin)," jER1031S "(tetraphenyl) Ethane type epoxy tree ) "YL7760" (bisphenol AF type epoxy resin) and the like.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. The range of 1: 0.1 to 1:10 is more preferable, and the range of 1: 0.3 to 1: 3 is more preferable.

  The content of the epoxy resin in the resin composition is preferably 10% by mass or more, more preferably, when the resin component is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good tensile fracture strength and insulation reliability. It is 25% by mass or more, more preferably 45% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(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, etc. An active ester compound having two or more ester groups having a high reaction activity per 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 preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one 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 Aromatic compounds having two or more active ester groups in one molecule, obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule, and having a phenolic hydroxyl group An aromatic compound obtained by reacting with an aromatic compound, and more preferably an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Moreover, if the carboxylic acid compound having at least two or more carboxy groups in a 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 the carboxylic acid compound 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, still more preferably 2 to 8 carbon atoms, specifically, acetic acid, malonic acid, succinic acid, maleic acid. An acid, itaconic acid, etc. are mentioned. The aromatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, and specific examples include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. . Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.

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

  As a phenol compound, C6-C40 is preferable, C6-C30 is more preferable, C6-C23 is still more preferable, C6-C22 is still more preferable, for example. Preferable specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Examples include cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene type diphenol. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used.

  As a naphthol compound, C10-C40 is preferable, for example, C10-C30 is more preferable, and C10-C20 is further more preferable. Preferable specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  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, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred, catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol More preferred are phosphorus, phosphorus atom-containing oligomers having phenolic hydroxyl groups, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenols, phosphorus having phenolic hydroxyl groups Atom-containing oligomers are particularly preferred, and dicyclopentadiene type diphenols are particularly preferred.

  The thiol compound is not particularly limited, and examples thereof include benzene dithiol and triazine dithiol.

  Preferable 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 product of phenol novolac, and a benzoylated product of phenol novolac. Examples include active ester compounds, active ester compounds obtained by reacting aromatic carboxylic acids and phosphorus atom-containing oligomers having phenolic hydroxyl groups. Among them, active ester compounds containing dicyclopentadiene-type diphenol structures, including naphthalene structures An active ester compound, an active ester compound obtained by reacting an aromatic carboxylic acid and a phosphorus atom-containing oligomer having a phenolic hydroxyl group is more preferred. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As the active ester compound, active ester compounds disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, and commercially available active ester compounds may also be used. As a commercial item of an active ester compound, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type diphenol structure manufactured by DIC) Active ester compound containing DIC, “EXB9416-70BK” (active ester compound containing naphthalene structure) manufactured by DIC, “DC808” (active ester compound containing acetylated phenol novolac) manufactured by Mitsubishi Chemical, Mitsubishi Chemical Corporation “YLH1026” (an active ester compound containing a benzoylated product of phenol novolak) manufactured by DIC, and “EXB9050L-62M” (a phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

  From the viewpoint of reducing 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 more preferably 20% by mass or more when the resin component is 100% by mass. Is more preferable. Although the upper limit of content of an active ester compound is not specifically limited, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 35 mass% or less is further more preferable.

  In addition, when the number of epoxy groups in (A) the epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of reactive groups in the (B) active ester compound is preferably 0.1 to 2, -1.5 is more preferable, and 0.3-1 is more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. The “reactive group” means a functional group capable of reacting with an epoxy group, and the “reactive group number of the active ester compound” means the solid content mass of the active ester compound present in the resin composition. This is the sum of all values divided by reactive group equivalents.

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

  (C) Polyamideimide resin is a polyamideimide resin having an alicyclic structure in the molecular structure from the viewpoint of compatibility with other components in the resin composition, and a siloxane structure described in JP-A No. 05-112760. It is preferable to use a polyamide-imide resin having a bulky branched chain structure, a polyamide-imide resin having an asymmetric monomer as a raw material, a polyamide-imide resin having a multi-branched structure, or the like.

  Among them, the viewpoint of improving the compatibility with the active ester compound (B) by having an isocyanuric ring structure, and the viewpoint of improving the compatibility and dispersibility of the resin varnish by the network structure by the branched isocyanuric ring structure (I) a polyamide-imide resin having an isocyanuric ring structure in the molecular structure (that is, a polyamide-imide resin having an isocyanuric ring structure and an imide skeleton or an amide skeleton) (ii) an isocyanuric ring structure and an alicyclic structure in the molecular structure A polyamideimide resin having a structure (that is, a polyamideimide resin having an isocyanuric ring structure, an alicyclic structure, and an imide skeleton or an amide skeleton), and (iii) having a repeating unit including an isocyanuric ring structure and an alicyclic structure Polyamideimide resin (ie, isocyanuric ring structure and alicyclic structure Polyamide-imide resin) is more preferred to contain a repeating unit containing a phagemid backbone or amide backbone, more preferably a polyamideimide resin (iii).

  As a preferred embodiment of the polyamideimide resin of (i) to (iii), (1) an isocyanuric ring-containing polyisocyanate compound derived from an alicyclic structure diisocyanate and a polycarboxylic acid having three or more carboxyl groups Carboxylic acid group-containing branched polyamideimide (hereinafter, the compound may be referred to as “(Compound C-1)”), (2) Compound (C— Carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter referred to as “compound (C-2)” which is a compound obtained by reacting 1) with a compound having one epoxy group and one or more radically polymerizable unsaturated groups. ) "Or (3) In the process of synthesizing the compound (C-1), one residual hydroxyl group and one or more radically polymerizable unsaturated atoms in the residual isocyanate group Is a compound obtained by reacting a compound having a group a carboxylic acid group-containing branched polymerizable polyamideimide (hereinafter referred to as "compound (C-3)".), And the like.

（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). In addition, let the repeating unit in the compound represented by general formula (I) be a repeating unit (I-1).

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

（式中、Ｒは式（Ｉ）中の残基を表す。） As the compound (C-2), a structure in which GMA (glycidyl methacrylate) is added to an arbitrary partial carboxyl group and / or terminal carboxyl group of the repeating unit (I-1) in the general formula (I) (I- And compound (II) having 2).

(In the formula, R represents a residue in formula (I).)

  The ratio of GMA modification of the carboxyl group is preferably in the range of adding GMA to the number of moles of the carboxyl group of the compound (C-1), preferably 0.3 mol% or more, more preferably 0.5 mol% or more, still more preferably 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), in the above formula (I), any part of the repeating unit (I-1) and / or the terminal imide group is an isocyanate residue, and the hydroxyl group of pentaerythritol triacrylate is added thereto. Compound (III) having the above structure (I-3) is exemplified.

(In the formula, R ′ represents a residue in formula (I).)

  The upper limit of the amount of addition of pentaerythritol triacrylate is preferably 40 mol%, more preferably 38 mol%, still more preferably 35 mol%, based on the number of moles of isocyanate groups of the polyisocyanate at the time of preparation. On the other hand, the lower limit of the amount of addition of pentaerythritol triacrylate is preferably 0.3 mol% with respect to the number of moles of the isocyanate group of the polyisocyanate at the time of charging, from the viewpoint of sufficiently obtaining the effect of addition. % Is more preferable, and 5 mol% is still more preferable.

  Polyamideimide resin can be synthesized by various known methods. As a method for synthesizing the polyamideimide resin, for example, the description in paragraphs 0020 to 0030 of International Publication No. 2010/074197 can be referred to, and the contents thereof 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. In addition, for example, compound (II) can be obtained by making glycidyl methacrylate react with "V-8000" made 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 thermal expansion coefficient. 2 mass% or more is more preferable, and 3 mass% or more is further more preferable. Although an upper limit is not specifically limited, 30 mass% or less is preferable, 20 mass% or less is more preferable, 15 mass% or less is further more preferable, and 10 mass% or less is still more preferable.

<(D) Inorganic filler>
The resin composition of 1st Embodiment contains (D) inorganic filler, and the average particle diameter of (D) inorganic filler is 100 nm or less. Moreover, the resin composition of 2nd Embodiment contains (D) inorganic filler, and the specific surface area of (D) inorganic filler is 15 m < ² > / g or more.

  The material of the inorganic filler is not particularly limited as long as it is an inorganic compound. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalc 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 thereof include bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle diameter of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably from the viewpoint of increasing the specific surface area of the inorganic filler and reducing the dielectric loss tangent and the linear thermal expansion coefficient. Is 80 nm or less. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 50 nm or more, More preferably, it is 60 nm or more, More preferably, it is 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 reducing the dielectric loss tangent and linear thermal expansion coefficient. More preferably, it is 80 nm or less. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 50 nm or more, More preferably, it is 60 nm or more, More preferably, it is 70 nm or more.
Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” and “UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd.

  The average particle diameter 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 can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba, Ltd., “SALD-2200” manufactured by Shimadzu Corporation, etc. can be used.

The specific surface area of the inorganic filler in the second embodiment is 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 the dielectric loss tangent and the linear thermal expansion coefficient. It is. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, More preferably, it is 50 m < ² > / g or less, More preferably, it is 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, and further preferably 30 m ² / g, from the viewpoint of reducing the dielectric loss tangent and the linear thermal expansion coefficient. That's it. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, More preferably, it is 50 m < ² > / g or less, More preferably, it is 40 m < ² > / g or less.
The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

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

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

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

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the 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% when the nonvolatile component in the resin composition is 100% by mass. It is at least mass%, at least 45 mass%, or at least 50 mass%. 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 the flame retardant include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, and the like, and phosphazene compounds are preferable. 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 having 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, for example, “SPH-100”, “SPS-100”, “SPB-100”, “SPE-100” manufactured by Otsuka Chemical Co., Ltd., “FP-100” manufactured by Fushimi Pharmaceutical Co., Ltd. “FP-110”, “FP-300”, “FP-400” and the like are mentioned, and “SPH-100” manufactured by Otsuka Chemical Co., Ltd. is preferable.

  Commercially available products may be used as the flame retardant other than the phosphazene compound, 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, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more when the resin component is 100% by mass. It is. The upper limit is preferably 6% by mass or less, more preferably 5% by mass or less, and still more preferably 4% by mass or less.

<(F) Hardener (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 the epoxy resin (A). For example, a phenol curing agent, a naphthol curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (F) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, a carbodiimide curing agent, and a cyanate ester curing agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” manufactured by DIC, and the like can be mentioned.

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

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

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

  When the resin composition contains (F) curing agent, the amount ratio of (A) epoxy resin to (F) curing agent is [(A) total number of epoxy groups of epoxy resin]: [(F) curing The ratio of the total number of reactive groups in 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 preferable. Here, the reactive group of (F) curing agent is an active hydroxyl group or the like, and varies depending on the type of (F) curing agent. Further, the total number of reactive groups in (F) curing agent is a value obtained by totaling the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all (F) curing agents.

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

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

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

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2. -Phenylimidazole is preferred.

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

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

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

  When the resin composition contains 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 0.00% when the resin component is 100% by mass. 5 mass% is more preferable and 0.01 mass%-0.3 mass% is still more preferable.

<(H) Thermoplastic resin>
In one embodiment, the resin composition may contain (H) a thermoplastic resin as long as the effects of the present invention are not impaired. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, A polyester resin is mentioned. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by NS ”,“ YL6794 ”,“ YL7213 ”,“ YL7290 ”,“ YL7482 ”, and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

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

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

  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 preferably 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 more preferable.

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

  As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles. As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan, “AC3401N” and “AC3816N” manufactured by Aika Industry.

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

<Physical properties and uses of resin composition>
The resin composition of the present invention can provide an insulating layer with good embedding property, low dielectric loss tangent, and excellent thermal expansion coefficient. 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. For example, a resin composition for forming an insulating layer of a printed wiring board As a resin composition (resin composition for an interlayer insulating layer of a printed wiring board) that can be suitably used as (resin composition for an insulating layer of a printed wiring board) and to form an interlayer insulating layer of a printed wiring board It can be used more suitably. Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

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

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

  A cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes exhibits a characteristic that the coefficient of linear thermal expansion (CTE) is low. That is, an insulating layer having a low linear thermal expansion coefficient is provided. As a linear thermal expansion coefficient, Preferably it is 35 ppm or less, More preferably, it is 33 ppm or less, More preferably, it is 30 ppm or less. The lower limit is not particularly limited, but may be 1 ppm or more. The linear thermal expansion coefficient (CTE) can be measured according to the method described in <Measurement of dielectric loss tangent and linear thermal expansion coefficient (CTE)> described later.

  The melt viscosity at 120 ° C. of the resin composition is preferably 6000 poise or less, more preferably 5000 poise or less, and 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 when the resin composition layer is thin. The melt viscosity can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of melt viscosity> described later.

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

  The thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, even more preferably 20 μm or less, 15 μm or less, or 10 μm or less, from the viewpoint of thinning the printed wiring board. is there. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 3 micrometers or more, etc.

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

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

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

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

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

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

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

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

  Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone, and acetates 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 performed by a known method such as heating or hot air blowing. Although drying conditions are not specifically limited, it is made to dry so that content of the organic solvent in a resin composition layer may be 4 mass% or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the resin sheet, a protective film according 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 a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  The resin composition layer exhibits characteristics that the melt viscosity can be lowered even if the amount of residual solvent is small. Therefore, an insulating layer with good embedding 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 more preferably 3.7% or less. The lower limit is not particularly limited, but may be 0.1% or more. The residual solvent amount can be measured according to the method described in <Measurement of residual solvent amount> described later.

  In addition, since the resin composition layer contains a polyamideimide resin, even if an inorganic filler having an average particle size of 100 nm or less is included, the embedding property is excellent and the generation of voids is suppressed. For example, even when three arbitrarily set 1 cm squares on a wiring pattern are observed on a 255 × 340 mm size substrate manufactured using the resin composition layer in the present invention, an appearance defect (diameter of 10 μm or more) ( There is no void. Presence / absence of voids can be measured by the method described in <Evaluation of presence / absence of voids> described later.

[Printed wiring board, printed wiring board manufacturing method]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is referred to as a wiring layer). is there).

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

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

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

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

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

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

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

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

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

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

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

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

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer in the steps (II) to (V). In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. Moreover, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

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

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

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

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

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

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

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

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

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

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

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

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

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Example 1: Production of resin composition 1>
8 parts of bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180), 15 parts of biphenyl type epoxy resin (“YX4000H” manufactured by Mitsubishi Chemical Corporation, about 190 equivalent of epoxy), 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 dissolved in 50 parts of methyl ethyl ketone (MEK) with stirring. After cooling to room temperature, 6 parts of hyperbranched polyamideimide resin (“ELG503” manufactured by DIC, n-butyl acetate solution with a solid content of 50% by mass), active ester compound (“HPC-8000-65T” manufactured by DIC) , Active group equivalent of about 223, solid solution of 65 mass% toluene solution), phenolic curing agent (“LA-3018-50P” manufactured by DIC), active group equivalent of about 151, 2-methoxypropanol with a solid content of 50% Solution) 10 parts, curing accelerator (4-dimethylaminopyridine (DMAP), 3 mass% MEK solution) 3 parts, spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm) , 75 parts of a specific surface area of 30.7 m ² / g) were mixed and dispersed uniformly with a high-speed rotary mixer, and then a cartridge filter (ROKITETECHNO) The resin composition 1 was produced by filtration through “SHP020”).

<Example 2: Production of resin composition 2>
In the preparation of the resin composition 1, 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) were added to an active ester compound (“DIC manufactured by DIC” EXB9416-70BK ", active group equivalent of about 274, solid content of 70% by weight methyl isobutyl ketone (MIBK) solution) 30 parts. A resin composition 2 was produced in the same manner as in the production of the resin composition 1 except for the above items.

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

<Example 4: Production of resin composition 4>
In the production of the 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 the hyperbranched polyamideimide resin (“DIC manufactured by DIC” ELG503 ", n-butyl acetate solution with a solid content of 50% by mass). A resin composition 4 was produced in the same manner as in the production of the resin composition 1 except for the above items.

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

<Example 6: Production of resin composition 6>
In the production of the 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 produced in the same manner as in the production of the resin composition 1 except for the above items.

<Example 7: Production of resin composition 7>
In the preparation of the resin composition 6, 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) were added to an active ester compound (“DIC” manufactured by “DIC” EXB9416-70BK ", an active group equivalent of about 274, and a MIBK solution with a solid content of 70% by mass). A resin composition 7 was produced in the same manner as in the production of the resin composition 1 except for the above items.

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

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

<Comparative Example 3: Production of Resin Composition 10>
In the production of the 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 produced in the same manner as in the production of the resin composition 8 except for the above items.

<Comparative Example 4: Production of resin composition 11>
In the preparation of the resin composition 8, 10 parts of phenoxy resin (Mitsubishi Chemical Corporation “YL7553BH30”, solid solution of 30% by mass of MEK and cyclohexanone 1: 1) was added to phenoxy resin (Mitsubishi Chemical Corporation “YL6954BH30”, solid (1: 1 solution of MEK and cyclohexanone of 30% by mass) was changed to 10 parts. A resin composition 11 was produced in the same manner as in the production of the resin composition 8 except for the above items.

<Comparative Example 5: Production of resin composition 12>
In the production of the resin composition 8, 10 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 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 with a solid content of 30% by mass) was changed to 10 parts. A resin composition 12 was produced in the same manner as in the production of the resin composition 8 except for the above items.

<Comparative Example 6: Production of resin composition 13>
In the production of the resin composition 8, 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, a toluene solution having an active group equivalent of about 223 and a solid content of 65% by mass) was added to an active ester compound (“DIC” manufactured by “DIC” EXB9416-70BK ", an active group equivalent of about 274, and a MIBK solution with a solid content of 70% by mass). A resin composition 13 was produced in the same manner as in the production of 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 die coater so that the thickness of the resin composition layer after drying is 7.5 μm on release PET, and dried at 70 to 95 ° C. for 2 minutes, A resin composition layer was obtained on the release PET. Next, 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 bonded to the resin composition layer on the surface not bonded to the support of the resin sheet. Laminated. Thereby, the resin sheet A which consists of order of mold release PET (support body), a resin composition layer, and a protective film was produced.

  Further, the resin sheet B is applied in the same manner as the resin sheet A except that the resin composition layer after drying is uniformly applied with a die coater so that the thickness of the resin composition layer becomes 40 μm and dried at 75 ° C. to 100 ° C. for 4 minutes. Produced.

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

(2) Lamination of resin sheet The protective film is peeled off from each resin sheet A prepared in advance, and a resin composition layer is obtained using a batch-type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700). Was laminated on both sides of the inner layer circuit board so as to be in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing for 45 seconds at 100 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed for 75 seconds at 100 ° C. and a pressure of 0.5 MPa.

(3) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet A is laminated is put into an oven at 100 ° C. for 30 minutes, then transferred to an oven at 180 ° C. and then thermoset for 30 minutes for insulation. A layer was formed and the release PET was peeled off to produce a void evaluation substrate.

(4) Evaluation of presence / absence of voids Using “DIGITAL MICROSCOPE KH-8700” manufactured by Hylox, three 1 cm squares arbitrarily set on the wiring pattern of the board for void evaluation were observed, and the diameter was 10 μm. The case where there were one or more voids which were the above appearance defects was designated as “X”, and the case where there were 0 voids was designated as “◯”. The absence of voids means excellent embedding.

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

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

(Measurement of linear thermal expansion coefficient (CTE))
A sample for evaluation of cured 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 load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) from 25 ° C. to 80 ° C. in the second measurement was calculated.

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

<Measurement of residual solvent amount>
Each resin sheet A prepared in advance was first cut into a 10 cm square, and its mass was measured (the measured mass is referred to as “A”). Next, the resin sheet A cut into 10 cm square was dried at 130 ° C. for 15 minutes, and the mass was measured again (the measured mass is referred to as “B”). Finally, 10 cm of PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) subjected to mold release treatment with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Corporation) used as a support. It cut out into the corner and measured the mass (this measured mass is set to "C"). The amount of residual solvent was calculated | required by applying measured mass AC to the following formula | equation 1.
Residual solvent amount = (A−B) / (A−C) × 100 (Formula 1)

  The average particle diameter and specific surface area of the inorganic filler used for the 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 in a vial and dispersed with an ultrasonic wave for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size by the median diameter was calculated.

<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., Ltd.), the sample surface is adsorbed with nitrogen gas, and the specific surface area is calculated using the BET multipoint method. Was measured.

The components used for the preparation of the resin compositions 1 to 13 and their blending amounts (parts by mass), the presence or absence of voids, melt viscosity, residual solvent amount, dielectric loss tangent, and CTE results are shown in the following table. The abbreviations in the table below are as follows.
828US: bisphenol A type epoxy resin, epoxy equivalent of about 180, Mitsubishi Chemical Corporation ESN475V: naphthol type epoxy resin, epoxy equivalent of about 330, 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, DIC EXB-9416-70BK: active ester compound, active group equivalent of about 274, DIC ELG503: polyamideimide resin, DIC V-8000BM : Polyamideimide resin, DIC Corporation UFP-30: Spherical silica, average particle size 0.078 μm, Denki Kagaku Kogyo Co., Ltd. SPH-100: Phosphazene resin, Otsuka Chemical Co., Ltd. LA-3018-50P: Phenolic curing agent, activity Group equivalent about 151, D V-03 manufactured by company C: 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, YL7891BH30 manufactured by Mitsubishi Chemical Corporation : Phenoxy resin, manufactured by Mitsubishi Chemical Corporation

  In Examples 1 to 7, it was confirmed that even if the components (E) to (G) were not contained, the results were the same as those in the above examples although there were differences in the degree.

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

Claims (16)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) The resin composition whose average particle diameter of an inorganic filler is 100 nm or less. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyamideimide resin, and (D) an inorganic filler,
(D) The resin composition whose specific surface area of an inorganic filler is 15 m < ² > / g or more.   (C) The resin composition of Claim 1 or 2 which is 3 to 30 mass% when content of a component makes a resin component 100 mass%.   (D) The resin composition of any one of Claims 1-3 whose content of a component is 50 mass% or more when the non-volatile component in a resin composition is 100 mass%.   The resin composition according to any one of claims 1 to 4, wherein the component (C) has an isocyanuric ring structure.   (C) The resin composition of any one of Claims 1-5 in which a component has a repeating unit containing an isocyanuric ring structure and an alicyclic structure. The resin composition according to any one of claims 1 to 6, wherein the component (C) is represented by the following general formula (I).

(In the formula, n represents 0-15.)   The resin composition according to any one of claims 1 to 7, wherein the content of the component (B) is 15% by mass or more when the resin component is 100% by mass.   The resin composition according to any one of claims 1 to 8, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 8, 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 8, which is for forming an insulating layer for forming a conductor layer.   The resin sheet containing the resin composition layer formed with the support body and the resin composition of any one of Claims 1-11 provided on this support body.   The resin sheet of Claim 12 whose thickness of a resin composition layer is 15 micrometers or less.   The resin sheet of Claim 12 or 13 whose residual solvent amount in a resin composition layer is 4 mass% or less. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 11.   A semiconductor device comprising the printed wiring board according to claim 15.

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