JP6805518B2 - Resin composition, resin sheet, printed wiring board and semiconductor device - Google Patents

Description

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

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet PCs has been increasing, and along with this, the insulating material (insulating layer) for semiconductor packages used in these small electronic devices is also required to have higher functionality. ing.

It is known that such an insulating layer is formed by curing a resin composition (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-82535

By the way, since a certain level of flame retardancy is required for the wafer level chip size package or the insulating layer used for the wiring board provided with the embedded wiring layer, it is common to include a flame retardant in the resin composition. ..

However, when the resin composition layer contains a flame retardant, there is a problem that swelling occurs between the insulating layer and the conductor layer after the reflow treatment.

In addition to flame retardancy, the insulating layer is also required to suppress warpage of the package substrate and adhere to the conductor layer, but it satisfies the required suppression of warpage and adhesion to the conductor layer. The current situation is that it has not reached the point.

The present invention has been made to solve the above problems, and is a resin composition in which the occurrence of warpage is suppressed and excellent in flame retardancy, peel strength and reflow resistance; a resin sheet using the resin composition, The purpose of the present invention is to provide a printed wiring board and a semiconductor device.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、水酸基、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよいグリシジル基を表し、Ａは、それぞれ独立に単結合、置換基を有していてもよい炭素原子数６〜１０のアリーレン基、スルフォニル基、置換基を有していてもよい炭素原子数１〜６のアルキレン基、又はこれらの組み合わせからなる２価の基を表す。ｎは３〜２５の整数を表し、ｍ１及びｍ２は、それぞれ独立に１〜５の整数を表す。Ｒ^１、Ｒ^２、及びＡが複数存在する場合、Ｒ^１、Ｒ^２、及びＡは同一であってもよく、異なっていてもよい。ただし、Ｒ^１及びＲ^２の少なくとも１つは水酸基である。）
［４］ （ａ）成分が、ブタジエン構造単位、ポリシロキサン構造単位、（メタ）アクリレート構造単位、アルキレン構造単位、アルキレンオキシ構造単位、イソプレン構造単位、イソブチレン構造単位、及びポリカーボネート構造単位から選択される１種以上の構造単位を有する、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ （ａ）成分が、ガラス転移温度が２５℃以下の樹脂、及び２５℃で液状である樹脂から選択される１種以上である、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ （ａ）成分が、（ｂ）成分と反応し得る官能基を有する、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ （ａ）成分が、イミド構造単位を有する、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ （ａ）成分が、フェノール性水酸基を有する、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ 支持体と、該支持体上に設けられた、［１］〜［８］のいずれかに記載の樹脂組成物を含む樹脂組成物層と、を有する樹脂シート。
［１０］ ［１］〜［８］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、プリント配線板。
［１１］ ［１０］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a phosphazene compound.
The content of the component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass.
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass.
A resin composition having an elastic modulus of 18 GPa or less at 23 ° C. of a thermosetting product obtained by thermosetting the resin composition at 180 ° C. for 1 hour.
[2] The resin composition according to [1], wherein the component (d) has a phenolic hydroxyl group.
[3] The resin composition according to [1] or [2], wherein the component (d) is represented by the following formula (1).

(In the formula (1), R ¹ and R ² may independently have a hydrogen atom, a hydroxyl group, and a substituent, respectively, and may have an alkyl group having 1 to 6 carbon atoms and a substituent. Represents an alkoxy group having 1 to 6 carbon atoms or a glycidyl group which may have a substituent, and A represents a single bond or a glycidyl group which may have a substituent, respectively. It represents an arylene group, a sulfonyl group, an alkylene group having 1 to 6 carbon atoms which may have a substituent, or a divalent group consisting of a combination thereof. N represents an integer of 3 to 25, and m1 and m2 independently represents an integer of 1 to 5. When a plurality of R ¹ , R ² , and A are present, R ¹ , R ² , and A may be the same or different. However, at least one of R ¹ and R ² is a hydroxyl group.)
[4] The component (a) is selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of [1] to [3], which has one or more structural units.
[5] The composition according to any one of [1] to [4], wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. Resin composition.
[6] The resin composition according to any one of [1] to [5], wherein the component (a) has a functional group capable of reacting with the component (b).
[7] The resin composition according to any one of [1] to [6], wherein the component (a) has an imide structural unit.
[8] The resin composition according to any one of [1] to [7], wherein the component (a) has a phenolic hydroxyl group.
[9] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [8].
[10] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[11] A semiconductor device including the printed wiring board according to [10].

According to the present invention, a resin composition in which the occurrence of warpage is suppressed and excellent in flame retardancy, peel strength and reflow resistance; a resin sheet, a printed wiring board, and a semiconductor device using the resin composition are provided. Can be done.

FIG. 1 is a schematic view showing an example of a cross section of a component temporary mounting inner layer substrate.

Hereinafter, the resin composition, the resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition containing (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a phosphazene compound, and (a). The content of the component is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass, and the content of the component (c) is the resin composition. When the non-volatile component is 100% by mass, it is 50% by mass to 95% by mass, and the elastic coefficient of the thermosetting product obtained by thermosetting the resin composition at 180 ° C. for 1 hour at 23 ° C. is 18 GPa or less.

From the viewpoint of suppressing the occurrence of warpage and improving flame retardancy, peel strength and reflow resistance, the resin composition of the present invention comprises (a) an elastomer and (b) an epoxy resin having an aromatic structure. , (C) Inorganic filler, and (d) Phosphazenic compound. The resin composition may further contain (e) a curing agent, (f) a curing accelerator, and (g) other additives, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Elastomer>
The resin composition comprises (a) an elastomer. In the present invention, the elastomer means a flexible resin, and is not particularly limited, but for example, in the molecule, a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, and an alkyleneoxy structural unit. , An isoprene structural unit, an isobutylene structural unit, and a resin that exhibits flexibility by having one or more structures selected from the polycarbonate structural unit. By including a flexible resin such as the component (a), the plating peel strength against copper and the like can be improved, and the occurrence of warpage and the like can be suppressed.

More specifically, the component (a) is a butadiene structural unit such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structural unit such as silicone rubber, a (meth) acrylate structural unit, and an alkylene structural unit (preferably having 2 to 2 carbon atoms). 15, more preferably 3 to 10 carbon atoms, still more preferably 5 to 6 carbon atoms), alkyleneoxy structural unit ((preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, still more preferable). Has one or more structural units selected from 5-6) carbon atoms, isoprene structural units, isobutylene structural units, and polycarbonate structural units, preferably butadiene structural units, polysiloxane structural units, ( It preferably has one or more structural units selected from meta) acrylate structural units, isoprene structural units, isobutylene structural units, or polycarbonate structural units, and is selected from butadiene structural units, (meth) acrylate structural units. It is more preferable to have one or more structural units. The “(meth) acrylate” refers to methacrylate and acrylate.

The component (a) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,00,000. It is 000. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (a) is preferably one or more resins selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. in order to exhibit flexibility.

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be −15 ° C. or higher. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, and more preferably a resin that is liquid at 15 ° C. or lower.

The component (a) is not particularly limited as long as it is a flexible resin, but it is preferable to have a functional group capable of reacting with the component (b) described later. The functional groups that can react with the component (b) include functional groups that appear by heating.

In one preferred embodiment, the functional group capable of reacting with component (b) comprises the group consisting of a hydroxy group (more preferably a phenolic hydroxyl group), a carboxy group, an acid anhydride group, an epoxy group, an isocyanate group and a urethane group. One or more functional groups of choice. Among them, as the functional group, a hydroxy group, an acid anhydride group, an epoxy group and an isocyanate group are preferable, and a hydroxy group, an acid anhydride group and an epoxy group are more preferable. However, when an epoxy group is contained as a functional group, the component (a) does not have an aromatic structure.

A preferred embodiment of the component (a) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower, and is preferably a hydride polybutadiene skeleton-containing resin (for example, a hydride polybutadiene skeleton-containing epoxy resin) or a hydroxy group-containing butadiene resin (more preferably phenolic). One or more resins selected from the group consisting of hydroxyl group-containing butadiene resin), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin. More preferable. Here, the "butadiene resin" refers to a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to 10,000. It is 15,000. Is. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxydated polybutadiene), "GQ-1000" manufactured by Nippon Soda Co., Ltd. (Filament, carboxyl group introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both terminal hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" (Both-terminal hydroxyl hydrogenated polybutadiene), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (with styrene) manufactured by Daicel Co., Ltd. Epoxy of butadiene and styrene block copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin), etc. manufactured by Nagase ChemteX Corporation. ..

Further, as another preferable embodiment of the component (a), a linear polyimide using a hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208) The polyimide described in No.) can also be used. The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

Another preferred embodiment of the component (a) is an acrylic resin. As the acrylic resin, an acrylic resin having a Tg of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin (more preferably a phenolic hydroxyl group-containing acrylic resin), a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group-containing acrylic resin are preferable. More preferably, one or more resins selected from the group consisting of acrylic resins, isocyanate group-containing acrylic resins and urethane group-containing acrylic resins. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5-34 mgKOH / g, weight average molecular weight 400,000-900,000, Tg-30-5 ° C), "SG-80H", "SG-80H-3", "SG" -P3 "(epoxy group-containing acrylic ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.)," SG-600TEA "," SG-790 "" (Hydroxy group-containing acrylic ester copolymer resin, hydroxyl value 20-40 mgKOH / g, weight average molecular weight 500,000-1.2 million, Tg-37-32 ° C), "ME-2000" manufactured by Negami Kogyo Co., Ltd. , "W-116.3" (carboxy group-containing acrylic acid ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin), "KG-25", "KG-3000" ( Epoxy group-containing acrylic acid ester copolymer resin) and the like.

Moreover, one preferable embodiment of the component (a) is a carbonate resin. The carbonate resin preferably has a glass transition temperature of 25 ° C. or lower, and is preferably a hydroxy group-containing carbonate resin (more preferably a phenolic hydroxyl group-containing carbonate resin), a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, or an epoxy group. One or more resins selected from the group consisting of a carbonate-containing resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin are preferable. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferable ranges are also the same.

Specific examples of the carbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Co., Ltd., and "C-1090", "C-2090" and "C-3090" manufactured by Kuraray Co., Ltd. (Polycarbonate diol) and the like.

Further, a linear polyimide (PCT / JP2016 / 053609) made from a hydroxy group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

Further, a preferred embodiment of the component (a) contains a polysiloxane resin, an alkylene resin, and an alkyleneoxy resin (for example, "YX-7180" manufactured by Mitsubishi Chemical Corporation (an alkylene structure having an ether bond). Resin)), isoprene resin, and isobutylene resin.

Specific examples of the polysiloxane resin are "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd. Examples thereof include amine group-terminated polysiloxane and linear polyimide (WO2010 / 053185) made from tetrabasic acid anhydride. Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Co., Ltd. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene block copolymer) manufactured by Kaneka Co., Ltd. ..

Further, preferred embodiments of the component (a) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (above, Kureha). (Made by Chemical Industry Co., Ltd.) and the like. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, and any flexible skeleton such as polyamide-imide. Specifically, VESTOSINT 2070 (Daiselhurus Co., Ltd.) ), SP500 (manufactured by Toray Industries, Inc.) and the like.

The content of the component (a) in the resin composition is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass from the viewpoint of imparting flexibility. It is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less. The lower limit is preferably 35% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more.

<(B) Epoxy resin having an aromatic structure>
The resin composition contains (b) an epoxy resin having an aromatic structure. The epoxy resin having an aromatic structure (hereinafter, also simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

Examples of the epoxy resin having an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, and naphthol. Novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin having aromatic structure, aromatic structure Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, alicyclic type having aromatic structure Epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, Examples thereof include a tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination. The component (b) is more preferably one or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin, and bisphenol F type epoxy resin and naphthalene. It is more preferably a type epoxy resin.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, one molecule has two or more epoxy groups, and a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and one molecule have three or more epoxy groups. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure and epoxy resin having a butadiene structure having an aromatic structure are preferable, and bisphenol A Type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are further preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US", "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A). Type epoxy resin), "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumitomo Metal Chemical ( "ZX1059" manufactured by Nagase ChemteX Corporation (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin), manufactured by Daicel Co., Ltd. "Ceroxide 2021P" (alicyclic epoxy resin having an ester skeleton), "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the liquid epoxy resin, an epoxy resin having two or more epoxy groups in one molecule and having a liquid aromatic ring structure at a temperature of 20 ° C. is preferable, and as a solid epoxy resin, three or more epoxys in one molecule. An epoxy resin having a group and having a solid aromatic ring structure at a temperature of 20 ° C. is preferable.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthic are preferable. Lene ether type epoxy resin is more preferable, and naphthalene type tetrafunctional epoxy resin and naphthylene ether type epoxy resin are further preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., Ltd. (Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (Dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumitomo Metal "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) manufactured by Kagaku Co., Ltd., "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd. (Bixylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), " 157S70 "(bisphenol novolac type epoxy resin)," YX4000HK "(bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.," YX8800 "(anthracene type epoxy resin)," PG-100 "manufactured by Osaka Gas Chemical Co., Ltd. , "CG-500", "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, their quantity ratio (solid epoxy resin: liquid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is in the range of 1: 0.3 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That is all. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

In the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the 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. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(C) Inorganic filler>
The resin composition contains (c) an inorganic filler. The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titnate phosphate and the like. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, from the viewpoint of improving circuit embedding property and obtaining an insulating layer having low surface roughness. It is preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd., and Denki Kagaku Kogyo Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex Co., Ltd. "SC2500SQ", "SO-C6", "SO" -C4 "," SO-C2 "," SO-C1 "and the like can be mentioned.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. It is preferable that the treatment is performed with one or more surface treatment agents such as. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type) manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent) and the like.

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, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. preferable.

The amount of carbon per unit surface area of the 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 a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The content of the inorganic filler in the resin composition is 50% by mass to 95% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. It is preferably 55% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, 70% by mass or more, or 75% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 87% by mass or less, still more preferably 85% by mass or less, from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

<(D) Phosphazen compound>
The resin composition comprises (d) a phosphazene compound. By including the component (d), the occurrence of warpage is suppressed, and it becomes possible to provide a resin composition having excellent flame retardancy, peel strength and reflow resistance.

The component (d) is not particularly limited as long as it is a cyclic compound containing nitrogen and phosphorus as constituent elements, but the component (d) is preferably a phosphazene compound having a phenolic hydroxyl group. Having a phenolic hydroxyl group facilitates the reaction of the component (d) with the component (a) and / or the component (b) (hereinafter, also referred to as “component (a) or the like”). When the component (d) reacts with the component (a) or the like, a three-dimensional crosslinked structure composed of the component (d) and the component (a) or the like is formed, and the peel strength and the reflow resistance become excellent. Further, by having a phenolic hydroxyl group, the compatibility with the component (a) and the like is increased even at a high temperature, and not only the flame retardancy but also the appearance after the reflow treatment is improved.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、水酸基、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよいグリシジル基を表し、Ａは、それぞれ独立に単結合、置換基を有していてもよい炭素原子数６〜１０のアリーレン基、スルフォニル基、置換基を有していてもよい炭素原子数１〜６のアルキレン基、又はこれらの組み合わせからなる２価の基を表す。ｎは３〜２５の整数を表し、ｍ１及びｍ２は、それぞれ独立に１〜５の整数を表す。Ｒ^１、Ｒ^２、及びＡが複数存在する場合、Ｒ^１、Ｒ^２、及びＡは同一であってもよく、異なっていてもよい。ただし、Ｒ^１及びＲ^２の少なくとも１つは水酸基である。） Among them, the component (d) is preferably a phosphazene compound represented by the following formula (1).

(In the formula (1), R ¹ and R ² may independently have a hydrogen atom, a hydroxyl group, and a substituent, respectively, and may have an alkyl group having 1 to 6 carbon atoms and a substituent. Represents an alkoxy group having 1 to 6 carbon atoms or a glycidyl group which may have a substituent, and A represents a single bond or a glycidyl group which may have a substituent, respectively. It represents an arylene group, a sulfonyl group, an alkylene group having 1 to 6 carbon atoms which may have a substituent, or a divalent group consisting of a combination thereof. N represents an integer of 3 to 25, and m1 and m2 independently represents an integer of 1 to 5. When a plurality of R ¹ , R ² , and A are present, R ¹ , R ² , and A may be the same or different. However, at least one of R ¹ and R ² is a hydroxyl group.)

The alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. Alkyl group of is more preferred. The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, but a linear or branched alkyl group is preferable. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group and the like. Can be mentioned.

The alkoxy group having 1 to 6 carbon atoms represented by R ¹ and R ² is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. Alkoxy group of is more preferable. Examples of alkyl groups having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group and hexyloxy. The group etc. can be mentioned. The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, but a linear or branched alkoxy group is preferable.

The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the glycidyl group represented by R ¹ and R ² may have a substituent.

The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-. Examples thereof include a ₁₀ aryl group, -NH ₂ , -CN, -C (O) O-C _1-6 alkyl group, -COOH, -C (O) H, -NO _{2 and the} like.

Here, the term "C _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, the expression "C _1-6 alkyl group" indicates an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

Examples of the arylene group having 6 to 10 carbon atoms represented by A include a phenylene group and a naphthylene group.

The alkylene group having 1 to 6 carbon atoms represented by A is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 1 to 3 carbon atoms. More preferred. The alkylene group having 1 to 6 carbon atoms may be linear, branched or cyclic, but a linear or branched alkylene group is preferable. Examples of alkylene groups having 1 to 6 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, dimethylmethylene group, n-butylene group, t-butylene group, pentylene group, neopentylene group and hexylene. Examples include a group and a cyclohexylene group.

From an arylene group having 6 to 10 carbon atoms which may have a substituent, a sulfonyl group, an alkylene group having 1 to 6 carbon atoms which may have a substituent, or a combination thereof represented by A. The divalent group is not particularly limited, and examples thereof include a phenylsulfonyl group, a 4-hydroxyphenylsulfonyl group, a phenyldimethylmethylene group, and a 4-hydroxyphenyldimethylmethylene group.

The arylene group having 6 to 10 carbon atoms and the alkylene group having 1 to 6 carbon atoms represented by A may have a substituent. The substituent has the same meaning as the substituent that the alkyl group have 1 to 6 carbon atoms represented by R ^1, and preferred ranges are also the same.

n represents an integer of 3 to 25, preferably an integer of 3 to 15, more preferably an integer of 3 to 10, and even more preferably 3.

m1 and m2 each independently represent an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2. Is particularly preferable.

（式（２）中、Ｒ^１１及びＲ^２１は、それぞれ独立に水素原子、水酸基、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよいグリシジル基を表す。ｎ１は３〜２５の整数を表す。ただし、Ｒ^１１及びＲ^２１の少なくとも１つは水酸基である。） Further, the component (d) is preferably a phosphazene compound represented by the following formula (2).

(In the formula (2), R ¹¹ and R ²¹ may independently have a hydrogen atom, a hydroxyl group, and a substituent, respectively, and may have an alkyl group having 1 to 6 carbon atoms and a substituent. Represents an alkoxy group having 1 to 6 carbon atoms or a glycidyl group which may have a substituent. N1 represents an integer of 3 to 25. However, at least one of R ¹¹ and R ²¹ is a hydroxyl group. .)

R ¹¹ and R ²¹ have the same meaning as R ¹ and R ² in the formula (1), and the preferable range is also the same. n1 is synonymous with n in the formula (1), and the preferred range is also the same.

（式（３）及び式（４）中、ｎ２は３から２５の整数を表す。）

Specific examples of the component (d) include, but are not limited to, a phosphazene compound having the following structure.

(In equations (3) and (4), n2 represents an integer from 3 to 25.)

As the component (d), a commercially available product may be used. For example, Otsuka Chemical Co., Ltd., "SPH-100", "SPS-100", "SPB-100", "SPE-100", Fushimi Pharmaceutical Co., Ltd. Examples thereof include "FP-100", "FP-110", "FP-300", "FP-400" manufactured by Otsuka Chemical Co., Ltd., and "SPH-100" manufactured by Otsuka Chemical Co., Ltd. is preferable.

The content of the component (d) is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less. The lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.

<(E) Hardener>
The resin composition may contain (e) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (b). For example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. The component (e) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based 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. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" , "KA-1160", "KA-1163", "KA-1165", "GDP-6115L", "GDP-6115H" manufactured by Gunei Chemical Co., Ltd. and the like.

An active ester-based curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer. The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, as an active ester compound containing an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" as an active ester-based curing agent which is an acetylated product of phenol novolac. (Made by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" as an active ester-based curing agent that is a benzoyl compound of phenol novolac (Manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A disicanate) manufactured by Lonza Japan Co., Ltd. Prepolymers in which some or all of them are triazined to form a trimer) and the like.

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

The content of the curing agent in the resin composition is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more.

<(F) Curing accelerator>
The resin composition may contain (f) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. 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. Examples thereof include an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the total amount of the non-volatile component of the component (b) and the curing agent is 100% by mass.

<(G) Arbitrary additive>
The resin composition may further contain other additives, if necessary, and such other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds. In addition, resin additives such as binders, thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants can be mentioned.

From the viewpoint of suppressing warpage, the resin composition of the present invention has an elastic modulus of 18 GPa or less, preferably 15 GPa or less, preferably 13 GPa or 11 GPa, of a thermosetting product heat-cured at 180 ° C. for 1 hour at 23 ° C. Below, it is more preferably 10 GPa or less, 9 GPa or less, or 8 GPa or less. The lower limit is not particularly limited, but may be, for example, 0.01 GPa or more, 0.5 GPa or more, 1 GPa or more, and the like. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

The cured product of the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes) has a characteristic that the occurrence of warpage is suppressed. Shown. The size of the warp is preferably less than 1 cm, more preferably 0.8 cm or less, still more preferably 0.5 cm or less. The evaluation of warpage can be measured according to the method described in <Evaluation of warpage> described later.

The cured product of the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 180 ° C. for 90 minutes) exhibits good peel strength. That is, it provides an insulating layer showing good peel strength. The peel strength of the cured resin composition is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, still more preferably 0.8 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The evaluation of the peel strength can be performed according to the method described in <Measurement of Peel Strength> described later.

The cured product of the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 180 ° C. for 90 minutes) exhibits good reflow resistance. That is, it provides an insulating layer showing good reflow resistance. It is preferable that the peel strength of the cured resin composition does not swell with the copper foil even if it is passed through a reflow device that reproduces the solder reflow temperature three times. The evaluation of reflow resistance can be measured according to the method described in <Appearance evaluation after reflow> described later.

The cured product of the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 190 ° C. for 90 minutes) exhibits a characteristic of excellent flame retardancy. The flame retardancy is preferably "V-0" or better according to the UL flame resistance test standard (UL-94). The evaluation of flame retardancy can be measured according to the method described in <Evaluation of flame retardancy> described later.

[Resin sheet]
The resin sheet of the present invention comprises a support and a resin composition layer bonded to the support, and the resin composition layer is formed from the resin composition of the present invention.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 50 μm or less or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonates (hereinafter sometimes abbreviated as "PC"), acrylic polymers such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfides (PES), polys. Examples thereof include ether ketone and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be matted or corona-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7", "Lumilar T6AM" manufactured by Toray Industries, Inc., and the like.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

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

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

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

In the resin sheet, a protective film similar 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). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

Instead of the resin sheet of the present invention, a prepreg formed by impregnating a sheet-like fiber base material with the resin composition of the present invention may be used.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. In particular, since the plating depth can be suppressed to be small in the present invention, it is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[Printed circuit board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

For example, the printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet.
(I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in the step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate or the like, or one or both sides of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, the inner layer circuit board of the intermediate product in which the insulating layer and / or the conductor layer should be further formed when the printed wiring board is manufactured is also included in the "inner layer board" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner layer board with built-in parts may be used (the conductor layer is also called a wiring layer).

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

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

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

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

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

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

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

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 170 ° C. 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).

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

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support is performed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V).

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

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

Step (V) is a step of forming a conductor layer.

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

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

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

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

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

Since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

As a method of manufacturing such a circuit board with built-in parts,
(I) An inner layer substrate having first and second main surfaces facing each other and having a cavity penetrating between the first and second main surfaces is joined to the second main surface of the inner layer substrate. A process of preparing a component temporary attachment inner layer substrate, which includes a temporary attachment material and a component temporarily attached by the temporary attachment material inside the cavity of the inner layer substrate.
(Ii) A step of laminating the resin sheet of the present invention so that the resin composition layer is bonded to the first main surface of the inner layer substrate.
(Iii) A step of peeling the temporary attachment material from the second main surface of the inner layer substrate,
(Iv) includes a step of laminating the resin sheet so that the resin composition layer is bonded to the second main surface of the inner layer substrate, and (v) a step of thermosetting the resin composition layer.

As an example shown in FIG. 1, the component temporary mounting inner layer substrate 100 (also referred to as “cavity substrate”) has the first and second main surfaces 11 and 12 facing each other, and the first and second main surfaces thereof. The inner layer substrate 1 in which the cavity 1a penetrating between the surfaces is formed, the temporary attachment material 2 bonded to the second main surface 12 of the inner layer substrate 1, and the temporary attachment material 2 inside the cavity 1a of the inner layer substrate 1. Includes the part 3 temporarily attached by. The inner layer substrate 1 may include circuit wiring 4 such as via wiring and surface wiring.

The cavity formed in the inner layer substrate can be formed by a known method using, for example, a drill, a laser, plasma, an etching medium or the like in consideration of the characteristics of the inner layer substrate. A plurality of cavities may be formed at predetermined intervals, and the opening shape of the cavity is not particularly limited, and may be any shape such as a rectangle, a circle, a substantially rectangular shape, and a substantially circular shape.

The temporary attachment material is not particularly limited as long as it has an adhesive surface exhibiting sufficient adhesiveness to temporarily attach the component, and any conventionally known temporary attachment material may be used in the manufacture of the component built-in circuit board. Examples of the temporary attachment material include PFDKE-1525TT (polyimide film with adhesive) manufactured by Arisawa Seisakusho Co., Ltd. and UC series (UV tape for wafer dicing) manufactured by Furukawa Electric Co., Ltd.

The component is temporarily attached to the adhesive surface of the temporary attachment material exposed through the cavity. As the component, an appropriate electrical component may be selected according to desired characteristics, and examples thereof include passive components such as capacitors, inductors, resistors and multilayer ceramic capacitors, and active components such as semiconductor bare chips. The same component may be used for all cavities, or different components may be used for each cavity.

The step (ii) is a step of laminating the resin sheet of the present invention so that the resin composition layer is bonded to the first main surface of the inner layer substrate. The laminating conditions of the first main surface and the resin sheet are the same as the conditions of the above-mentioned step (I), and the preferable range is also the same.

After laminating the resin composition layer on the first main surface of the inner layer substrate, the resin composition layer may be heat-cured. The conditions for thermosetting the resin composition layer are the same as those in the above-mentioned step (II), and the preferable range is also the same.

The step (iii) is a step of peeling the temporary attachment material from the second main surface of the inner layer substrate. The temporary attachment material may be peeled off according to a conventionally known method depending on the type of temporary attachment material.

The step (iv) is a step of laminating the resin sheet so that the resin composition layer is bonded to the second main surface of the inner layer substrate. The laminating conditions of the second main surface and the resin sheet are the same as the conditions of the above-mentioned step (I), and the preferable range is also the same. The resin composition layer in the step (iv) may be the same resin composition layer as the resin composition layer in the step (ii), or may be a different resin composition layer.

The step (v) is a step of thermosetting the resin composition layer. The conditions for thermosetting the resin composition layer are the same as those in the above-mentioned step (II), and the preferable range is also the same.

As a method for manufacturing a circuit board with built-in components, further steps include a step of drilling holes in the insulating layer (drilling step), a step of roughening the surface of the insulating layer, and a step of forming a conductor layer on the surface of the roughened insulating layer. It may be included. These steps are as described above.

The printed wiring board of the present invention may include an insulating layer which is a cured product of the resin composition layer of the resin sheet of the present invention, and an embedded wiring layer embedded in the insulating layer.

As a method for manufacturing such a printed wiring board,
(1) A step of preparing a base material with a wiring layer having an inner layer substrate and a wiring layer provided on at least one surface of the base material.
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer and heat-curing it to form an insulating layer so that the wiring layer is embedded in the resin composition layer.
It includes (3) a step of connecting wiring layers between layers and (4) a step of removing a base material.

It is preferable to have a metal layer made of copper foil or the like on both sides of the inner layer substrate used in this manufacturing method, and it is more preferable that the metal layer has a structure in which two or more metal layers are laminated. The details of the step (1) are as follows: a dry film (photosensitive resist film) is laminated on an inner layer substrate, exposed and developed under predetermined conditions using a photomask to form a pattern dry film. A wiring layer is formed by an electric field plating method using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off.

The laminating conditions of the inner layer substrate and the dry film are the same as the conditions of the above-mentioned step (II), and the preferable range is also the same.

After laminating the dry film on the inner layer substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 18/18 μm or less (pitch 36 μm or less). More preferably, it is 15/15 μm or less (pitch 30 μm or less). The lower limit of the line / space ratio of the wiring layer is not particularly limited, but is preferably 0.5 / 0.5 μm or more, and more preferably 1/1 μm or more. The pitch does not have to be the same throughout the wiring layer.

After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, the formation of the wiring layer can be carried out by a plating method using a dry film having a desired pattern formed as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring 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 wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). Nickel alloys and copper-titanium alloys).

The thickness of the wiring layer depends on the desired design of the printed wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm.

After forming the wiring layer, the dry film is peeled off. The peeling of the dry film can be carried out by a known method. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern.

The step (2) is a step of laminating the resin sheet on the base material with the wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing the resin sheet to form an insulating layer. The laminating conditions of the base material with the wiring layer and the resin sheet are the same as the conditions of the above-mentioned step (II), and the preferable range is also the same.

The step (3) is not particularly limited as long as the wiring layers can be interconnected, but is a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer. It is preferable that the step is at least one of the above steps. The steps of forming the via holes in the insulating layer and forming the conductor layer are as described above.

The method for polishing or grinding the insulating layer is not particularly limited as long as the printed wiring layer can be exposed and the polishing or grinding surface is horizontal, and a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, a surface grinding method by rotating a grindstone, and the like can be mentioned.

The step (4) is a step of removing the inner layer substrate and forming the printed wiring board of the present invention. The method for removing the inner layer substrate is not particularly limited. In one preferred embodiment, the inner layer substrate is peeled from the printed wiring board at the interface of the metal layer on the inner layer substrate, and the metal layer is removed by etching with, for example, an aqueous solution of copper chloride.

In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when a resin sheet is used.

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

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Manufacturing of Elastomer A>
G-3000 (bifunctional hydroxy group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxy group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) 50 g in a reaction vessel. 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product is cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol are added to the reaction product. 40.4 g of acetate (manufactured by Daicel Co., Ltd.) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^-1 was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100 μm mesh filter cloth to obtain an elastomer A having a butadiene structure and an acid anhydride group.
Viscosity: 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value: 16.9 mgKOH / g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10 ° C
Content of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4% by mass
Functional group equivalent: 45943 g / eq

[Manufacturing Example 1: Production of Resin Varnish 1]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, phosphazene compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution), 4 parts, epoxy A 30 parts, phenylaminosilane system Spherical silica surface-treated with a coupling agent (Shinetsu Chemical Industry Co., Ltd., "KBM573") (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin ("KA-1163" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 1.

[Manufacturing Example 2: Production of Resin Varnish 2]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, phosphazene compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) 8 parts, epoxy A 30 parts, phenylaminosilane cup Spherical silica surface-treated with a ring agent (Shinetsu Chemical Industry Co., Ltd., "KBM573") (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin ( "KA-1163" manufactured by DIC Co., Ltd., 4 parts of phenolic hydroxyl group equivalent: 118 g / eq) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 2.

[Manufacturing Example 3: Production of Resin Varnish 3]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, Phosphazen compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) 4 parts, acrylic acid ester copolymer resin (Nagasechem) Tex Co., Ltd., "Taisan Resin SG-80H", solid content 20%, MEK / toluene solution, Tg 11 ° C, functional group equal amount 14285 g / eq, weight average molecular weight Mw 350,000) 75 parts, phenylaminosilane coupling agent Spherical silica surface-treated with (Shinetsu Chemical Industry Co., Ltd., "KBM573") (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC (DIC) "KA-1163" manufactured by KA Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq), 4 parts, and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 3.

[Manufacturing Example 4: Production of Resin Varnish 4]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, Phosphazen compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) 8 parts, acrylic acid ester copolymer resin (Nagasechem) Tex Co., Ltd., "Taisan Resin SG-80H", solid content 20%, MEK / toluene solution, Tg 11 ° C, functional group equal amount 14285 g / eq, weight average molecular weight Mw 350,000) 75 parts, phenylaminosilane coupling agent Spherical silica surface-treated with (Shinetsu Chemical Industry Co., Ltd., "KBM573") (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC (DIC) "KA-1163" manufactured by KA Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) (4 parts) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 4.

[Manufacturing Example 5: Production of Resin Varnish 5]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, 3 parts of "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts of naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, Phosphazen compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) 4 parts, Epoxy resin (Mitsubishi Chemical Co., Ltd.) , "YX7180BH40", solid content 40%, MEK / cyclohexanone solution) 37.5 parts, spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573") (Co., Ltd.) Admatex, "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC Co., Ltd. "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 4 parts, methyl ethyl ketone 15 parts Was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 5.

[Manufacturing Example 6: Production of Resin Varnish 6]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, 3 parts of "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts of naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, Phosphazen compound (Otsuka Chemical Co., Ltd., "SPH-100" solid content 50% cyclohexanone solution) 8 parts, Epoxy resin (Mitsubishi Chemical Co., Ltd.) , "YX7180BH40", solid content 40% MEK / cyclohexanone solution) 37.5 parts, spherical silica (Ad Co., Ltd.) surface-treated with a phenylaminosilane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573") Matex, "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC Co., Ltd. "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 4 parts, methyl ethyl ketone 15 parts The resin varnish 6 was prepared by mixing and uniformly dispersing with a high-speed rotating mixer.

[Manufacturing Example 7: Production of Resin Varnish 7]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 part, acrylic acid ester copolymer resin (Nagase Chemtex Co., Ltd., "Taisan Resin SG-80H", solid content 20%, MEK / toluene solution, Tg 11 ° C. , Functional group equal amount 14285 g / eq, weight average molecular weight Mw 350,000) 75 parts, spherical silica (Admatex Co., Ltd.) surface-treated with a phenylaminosilane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573") , "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC Co., Ltd. "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 4 parts, methyl ethyl ketone 15 parts mixed Then, the resin varnish 7 was produced by uniformly dispersing it with a high-speed rotating mixer.

[Manufacturing Example 8: Production of Resin Varnish 8]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, "JER806" manufactured by Mitsubishi Chemical Corporation, 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, manufactured by DIC Co., Ltd., "HP4032"), 3 parts, imidazole derivative (Shikoku) Kasei Co., Ltd., "2P4MZ") 0.05 parts, phosphorus compound (flame retardant, (Daihachi Kagaku Co., Ltd., "TPP", triphenyl phosphate), 3 parts, acrylic acid ester copolymer resin (Nagase) "Taisan Resin SG-80H" manufactured by Chemtex Co., Ltd., solid content 20%, MEK / toluene solution, Tg 11 ° C., functional group equal amount 14285 g / eq, weight average molecular weight Mw 350,000) 75 parts, phenylaminosilane coupling Spherical silica (manufactured by Admatex Co., Ltd., "SO-C5", average particle size 1.6 μm) 120 parts, cresol novolac resin (DIC) surface-treated with an agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573") "KA-1163" manufactured by KA Co., Ltd., phenolic hydroxyl group equivalent: 118 g / eq) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 8.

[Example 1: Preparation of resin sheet 1]
A resin varnish 1 is applied onto a polyethylene terephthalate film (thickness 75 μm, hereinafter abbreviated as “PET film”) with a die coater so that the thickness of the resin composition layer after drying is 40 μm, and 80 to 120 The resin sheet 1 was obtained by drying at ° C. (average 100 ° C.) for 10 minutes.

[Example 2: Preparation of resin sheet 2]
In Example 1, the resin varnish 1 was changed to the resin varnish 2. A resin sheet 2 was obtained in the same manner as in Example 1 except for the above items.

[Example 3: Preparation of resin sheet 3]
In Example 1, the resin varnish 1 was changed to the resin varnish 3. A resin sheet 3 was obtained in the same manner as in Example 1 except for the above items.

[Example 4: Preparation of resin sheet 4]
In Example 1, the resin varnish 1 was changed to the resin varnish 4. A resin sheet 4 was obtained in the same manner as in Example 1 except for the above items.

[Example 5: Preparation of resin sheet 5]
In Example 1, the resin varnish 1 was changed to the resin varnish 5. A resin sheet 5 was obtained in the same manner as in Example 1 except for the above items.

[Example 6: Preparation of resin sheet 6]
In Example 1, the resin varnish 1 was changed to the resin varnish 6. A resin sheet 6 was obtained in the same manner as in Example 1 except for the above items.

[Comparative Example 1: Preparation of Resin Sheet 7]
In Example 1, the resin varnish 1 was changed to the resin varnish 7. A resin sheet 7 was obtained in the same manner as in Example 1 except for the above items.

[Comparative Example 2: Preparation of Resin Sheet 8]
In Example 1, the resin varnish 1 was changed to the resin varnish 8. A resin sheet 8 was obtained in the same manner as in Example 1 except for the above items.

[Measurement of elastic modulus]
(Preparation of cured product for evaluation)
The untreated surface of the release PET film ("501010" manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square) is a glass cloth base material epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works Co., Ltd., thickness. It was placed on a glass cloth base material epoxy resin double-sided copper-clad laminate so as to be in contact with (0.7 mm, 255 mm square), and the four sides of the release film were fixed with polyimide adhesive tape (width 10 mm).

Each resin sheet (167 × 107 mm square) produced in Examples and Comparative Examples was used as a resin composition using a batch type vacuum pressurizing laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700). The layer was centrally laminated so that it was in contact with the release surface of the release PET film. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, the support was peeled off, and the resin composition layer was heat-cured at 180 ° C. for 1 hour.

After thermosetting, the polyimide adhesive tape was peeled off, and the resin composition layer was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled off from the resin composition layer to obtain a sheet-shaped cured product (evaluation cured product).

(Measurement of elastic modulus)
The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ° C. was determined. The measurement was carried out in accordance with JIS K7127. This operation was performed three times, and the average value is shown in the table.

[Evaluation of warpage]
(Preparation of evaluation board)
(1) Step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material (1-1) Lamination of a dry film on a base material (core substrate) As a core substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate (layer structure: Microsin MT-Ex copper foil (thickness 3 μm copper foil / thickness 18 μm carrier foil) manufactured by Mitsui Metal Mining Co., Ltd.) / Panasonic "R1515A" substrate manufactured by Mitsui Metal Mining Co., Ltd. (thickness 0.2 mm) / Microsin MT-Ex copper foil manufactured by Mitsui Metal Mining Co., Ltd. (carrier foil with a thickness of 18 μm / copper foil with a thickness of 3 μm)) 170 × 110 mm square Prepared. A dry film with a PET film (“ALPHO 20A263” manufactured by Nikko Materials Co., Ltd., dry film thickness 20 μm) is bonded to the copper foil on both sides of the laminated plate on the matte surface side of the 3 μm copper foil. As described above, the film was laminated using a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). The dry film was laminated by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then pressure-bonding the dry film at a temperature of 70 ° C. and a pressure of 0.1 MPa for 20 seconds.

(1-2) Pattern formation A glass mask (photomask) in which the wiring pattern shown below is formed is placed on a PET film which is a protective layer of a dry film, and is irradiated with a UV lamp at an irradiation intensity of 150 mJ / cm ² . UV irradiation was performed. After UV irradiation, the PET film of the dry film was peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed at an injection pressure of 0.15 MPa for 30 seconds. Then, it was washed with water and the dry film was developed (pattern formation).

Wiring pattern of glass mask:
Comb tooth patterns (wiring length 15 mm, 16 lines) with L / S = 15 μm / 15 μm, that is, a wiring pitch of 30 μm are formed at 10 mm intervals.

(1-3) Formation of Wiring Layer After the dry film was developed, electrolytic copper plating was performed to a thickness of 15 μm to form a wiring layer. Next, a 3% sodium hydroxide solution at 50 ° C. was spray-treated at an injection pressure of 0.2 MPa, the dry film was peeled off, washed with water, and dried at 150 ° C. for 30 minutes.

(2) A step of laminating a resin sheet on a base material with a wiring layer and thermosetting to form an insulating layer so that the wiring layer is embedded in the resin composition layer (2-1) Lamination of the resin sheet Examples and The protective film of the protective film (167 mm × 107 mm) of the resin sheet produced in the comparative example was peeled off, and a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) was used. The resin composition layer was embedded and laminated on both sides of the wiring layer so as to be bonded to the wiring layer. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 110 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was heat-pressed at 110 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it.

(2-2) Thermosetting of Resin Composition Layer After laminating the resin sheet, the support (PET film) is peeled off, and the resin composition layer is thermosetting under the conditions of 100 ° C. for 30 minutes and then 170 ° C. for 30 minutes. Insulation layers were formed on both sides of the wiring layer.

(3) Step of forming a via hole in the insulating layer A laser is irradiated from above the insulating layer from above the insulating layer using a CO ₂ laser machine "605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation. A via hole having a top diameter (75 μm) was formed in the insulating layer directly above the 150 μm square wiring layer, which is the land of the comb-tooth wiring pattern. The laser irradiation conditions were a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.36 mJ / shot, a number of shots of 3, and burst mode (10 kHz).

(3-1) Step of roughening treatment A desmear treatment was performed on a structure provided with via holes. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
The circuit board provided with the via hole was placed in a swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution ( "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally a neutralizing solution (Atotech Japan Co., Ltd.) ), "Reduction Solution Securigant P", aqueous sulfuric acid solution) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes.

(3-2) Step of forming a conductor layer (3-2-1) Electrolytic plating step In order to form a conductor layer on the surface of an evaluation substrate, a plating step including the following steps 1 to 6 (Atotech Japan Co., Ltd.) A conductor layer was formed by performing a copper plating step) using a chemical solution made in Japan.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
Product name: Cleaning was performed at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. 2. Soft etching (cleaning inside the via hole)
Treatment was carried out at 30 ° C. for 1 minute using an aqueous sodium sulfate-acidic peroxodisulfate solution.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
Treatment was performed at 35 ° C. for 5 minutes using Activator Neoganth 834 (trade name).
5. Reduction (Pd applied to the insulating layer is reduced)
Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
A mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35 ° C. Treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(3-2-2) Electroplating Step Next, an electrolytic copper plating step was performed under the condition that the via hole was filled with copper using a chemical solution manufactured by Atotech Japan Co., Ltd. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 150 μm corresponding to the via hole is formed (the portion without the via connection is also formed on the entire surface at a pitch of 600 μm), and this land pattern is used to form the surface of the insulating layer. A conductor layer having a conductor pattern with a thickness of 15 μm was formed on the surface. Next, the annealing treatment was performed at 190 ° C. for 90 minutes.

(4) Step of removing the base material After adhering a PET film with an adhesive (thickness 50 μm) to the entire surface of the base material with a wiring layer on which a conductor layer is formed, the micro-thin MT-Ex copper foil of the core substrate is used. A cutter blade was inserted into the interface between a copper foil having a thickness of 3 μm and a carrier foil having a thickness of 18 μm, and the core substrate was peeled off and separated. Next, the surface on which the conductor layer was formed was protected by a PET film with an adhesive, and a 3 μm copper foil was etched and removed with an aqueous solution of copper chloride, washed with water, and then dried at 110 ° C. for 30 minutes. Then, the PET film with an adhesive was peeled off to prepare a wiring board in which an L / S = 15/15 μm comb tooth pattern was embedded on one side. The obtained wiring board is referred to as "evaluation board A".

(5) Evaluation of warpage Of the four sides of the evaluation board A, one side is fixed to the SUS plate with an adhesive tape (product name, Kapton adhesive tape, manufactured by Teraoka Seisakusho Co., Ltd.) with a width of 107 mm, and the highest point from the SUS plate. The value of warpage was calculated by calculating the height. This operation was repeated 4 times, and the case where the average value of the warp was less than 1 cm was evaluated as “◯”, the case where the average value was 1 cm or more and less than 2 cm was evaluated as “Δ”, and the case where the average value was 2 cm or more was evaluated as “x”.

<Measurement of peel strength>
The resin sheets produced in Examples and Comparative Examples were laminated on a copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm), and then the PET film was removed. The obtained copper foil with resin was used as a glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, both sides of R5715ES manufactured by Matsushita Electric Industrial Co., Ltd. were roughened by MEC Co., Ltd. Laminated with a batch type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700") on a copper surface roughened by etching to 1 μm with a treatment agent (CZ8100). did. After that, it was thermoset at 180 ° C. for 90 minutes, and a notch with a width of 10 mm and a length of 100 mm was made in the prepared sample, and one end of the copper foil was peeled off to make a gripper (manufactured by TSE Co., Ltd., autocom type). It was grasped by a testing machine AC-50C-SL), and the load (kgf / cm (N / cm)) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.) was measured.

<Appearance evaluation after reflow>
The resin sheets produced in Examples and Comparative Examples were laminated on a copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm), and then the PET film was removed. The obtained copper foil with resin was used as a glass cloth base material, and both sides of an epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Industrial Co., Ltd.) were coarsely manufactured by MEC Co., Ltd. Laminated with a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) on a copper surface roughened by etching to 1 μm with a chemical treatment agent (CZ8100). did. Subsequently, it was heat-cured at 180 ° C. for 90 minutes, and the prepared sample was cut into 5 cm × 15 cm. A reflow device ("HAS-" manufactured by Nippon Antom Co., Ltd.) that reproduces the solder reflow temperature with a peak temperature of 260 ° C after making a notch in the part with a width of 10 mm and a length of 100 mm, peeling off one end of the copper foil and peeling off 35 mm. 6116 ") was passed three times (reflow temperature profile conforms to IPC / JEDEC J-STD-020C). Those in which no swelling occurred between the thermosetting product and the copper foil were designated as "○", and those in which swelling occurred were designated as "x".

<Evaluation of flame retardancy>
The resin sheets produced in Examples and Comparative Examples were repeatedly bonded together using a batch type vacuum pressure laminator MVLP-500 (manufactured by Meiki Co., Ltd.), and the thickness of the resin composition layer was 0.4 mm. A resin sheet having a composition of PET / resin composition layer / PET was prepared. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. After peeling one PET film from the resin sheet, the resin composition layer was cured under curing conditions of 190 ° C. for 90 minutes. After curing, the other PET film was peeled off, the resin composition layer was taken out, cut into a size of 12.7 mm × 127 mm for UL flame retardancy test, and the end face was polished with sandpaper (# 1200 and then # 2800). The pieces were treated in an oven at 70 ± 1 ° C. for 168 hours, then allowed to cool in a desiccator for 4 hours or more, and the flame retardancy was evaluated according to the UL flame resistance test standard (UL-94). For details, the burner was moved directly under the obtained test piece, the flame was indirectly flamed in the center of the lower end of the test piece for 10 seconds, and the subsequent burning time was measured. Indirect flame was applied again for 10 seconds, and the subsequent burning time was measured. This was repeated 5 times and evaluated based on the following criteria.
(Evaluation criteria)
V-0: No fall of combustibles, no burning of test piece, burning time of test piece is 50 seconds or less V-1: No falling of combustible, no burning of test piece, burning time of test piece is 50 seconds Exceeded 250 seconds or less Not: Combustion falls, test piece burns out, or test piece burn time exceeds 250 seconds

100 Temporary mounting of parts Inner layer board (cavity board)
1 Inner layer board 1a Cavity 11 First main surface 12 Second main surface 2 Temporary attachment material 3 Parts 4 Circuit wiring

Claims (12)

A resin composition containing (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a phosphazene compound.
The content of the component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass.
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass.
The elastic modulus of the thermosetting product obtained by thermally curing the resin composition at 180 ° C. for 1 hour at 23 ° C. is 18 GPa or less.
(A) A resin composition in which the component has an imide structural unit. A resin composition containing (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a phosphazene compound.
The content of the component (a) is 55 % by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass.
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass.
A resin composition having an elastic modulus of 18 GPa or less at 23 ° C. of a thermosetting product obtained by thermosetting the resin composition at 180 ° C. for 1 hour. The resin composition according to claim 2, wherein the component (a) has an imide structural unit. The resin composition according to any one of claims 1 to 3, wherein the component (d) has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 4, wherein the component (d) is represented by the following formula (1).

(In the formula (1), R ¹ and R ² may independently have a hydrogen atom, a hydroxyl group, and a substituent, respectively, and may have an alkyl group having 1 to 6 carbon atoms and a substituent. Represents an alkoxy group having 1 to 6 carbon atoms or a glycidyl group which may have a substituent, and A represents a single bond or a glycidyl group which may have a substituent, respectively. It represents an arylene group, a sulfonyl group, an alkylene group having 1 to 6 carbon atoms which may have a substituent, or a divalent group consisting of a combination thereof. N represents an integer of 3 to 25, and m1 and m2 independently represents an integer of 1 to 5. When a plurality of R ¹ , R ² , and A are present, R ¹ , R ² , and A may be the same or different. However, at least one of R ¹ and R ² is a hydroxyl group.) One or more of the components (a) selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of claims 1 to 5, which has the structural unit of. The resin composition according to any one of claims 1 to 6, wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. .. The resin composition according to any one of claims 1 to 7, wherein the component (a) has a functional group capable of reacting with the component (b). Any one of claims 1 to 8, wherein the component (a) has one or more functional groups selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to the section. A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 9. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device including the printed wiring board according to claim 11.

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