JP7067111B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a circuit board, and a semiconductor chip package obtained by using the resin composition.

In recent years, the miniaturization and high performance of electronic devices have progressed, and in semiconductor package substrates, build-up layers have been made into multiple layers, and there is a demand for finer wiring and higher densities. Further, with the spread of smartphones and tablet PCs, the demand for thinning is increasing, and there is a need for thinning of core materials and thin package substrates such as coreless structures. These materials are required to have characteristics such as a low coefficient of thermal expansion. The resin composition used for forming the insulating layer used for these materials is considered to contain a large amount of an inorganic filler in order to have a low coefficient of thermal expansion, but a large amount of the inorganic filler is used. In the resin composition contained therein, the cured body of the resin composition becomes brittle, so that problems such as resin chipping of the cured body may occur from the end when handling the package substrate.

For example, Patent Document 1 provides a thermosetting resin composition containing a phenolic curing agent or the like, which can prevent resin chipping even though the linear thermal expansion coefficient is low.

Japanese Unexamined Patent Publication No. 2014-15608

The present invention provides a resin composition suitable for forming an insulating layer used for a build-up layer of a wiring board which has been made denser, thinner, or coreless, a wafer level chip size package, or the like. Yes, specifically, a resin composition capable of obtaining an insulating layer having excellent shear strength, breaking bending strain, and crack resistance, and having a low dielectric constant contact and a low specific dielectric constant; obtained by using the resin composition. It is an object of the present invention to provide a resin sheet, a circuit board, and a semiconductor chip package.

As a result of diligent studies to solve the above problems, the present inventors have made the resin composition contain an epoxy resin, an inorganic filler, and a predetermined novolak-type phenol resin to provide a shear strength, a breaking bending strain, and a resistance to bending. We have found that it is possible to obtain an insulating layer having excellent crackability and a low dielectric constant contact and a low relative permittivity, and have completed the present invention.

（一般式（１）中、Ｒ¹は、炭素原子数８以上の１価の炭化水素基を表す。）
［２］ （Ｂ）成分の含有量が、樹脂組成物中の不揮発成分を１００質量％とした場合、３０質量％以上９５質量％以下である、［１］に記載の樹脂組成物。
［３］ （Ｃ）成分の含有量が、樹脂組成物中の樹脂成分１００質量％とした場合、１質量％以上１５質量％以下である、［１］又は［２］に記載の樹脂組成物。
［４］ （Ａ）成分が、（Ａ－１）窒素含有エポキシ樹脂又は縮合環構造を有するエポキシ樹脂を含有する、［１］～［３］のいずれかに記載の樹脂組成物。
［５］ （Ａ）成分が、さらに（Ａ－２）（Ａ－１）成分以外の２５℃で液状のエポキシ樹脂を含む、［４］に記載の樹脂組成物。
［６］ （Ａ－１）成分と（Ａ－２）成分との量比（（Ａ－１）成分：（Ａ－２）成分）が、１：０．１～１：１０の関係を満たす、［５］に記載の樹脂組成物。
［７］ さらに、（Ｄ）熱可塑性樹脂を含有する、［１］～［６］のいずれかに記載の樹脂組成物。
［８］ 半導体チップパッケージの絶縁層用樹脂組成物である、［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］～［７］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］ 半導体チップパッケージの絶縁層用樹脂シートである、［９］に記載の樹脂シート。
［１１］ ［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、回路基板。
［１２］ ［１１］に記載の回路基板と、該回路基板上に搭載された半導体チップとを含む、半導体チップパッケージ。
［１３］ ［１］～［８］のいずれかに記載の樹脂組成物、もしくは［９］に記載の樹脂シートにより封止された半導体チップを含む半導体チップパッケージ。 That is, the present invention includes the following contents.
[1] (A) Epoxy resin,
A resin composition containing (B) an inorganic filler and (C) a novolak-type phenolic resin containing a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 8 or more carbon atoms.)
[2] The resin composition according to [1], wherein the content of the component (B) is 30% by mass or more and 95% by mass or less when the non-volatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the content of the component (C) is 1% by mass or more and 15% by mass or less when the content of the resin component in the resin composition is 100% by mass. ..
[4] The resin composition according to any one of [1] to [3], wherein the component (A) contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure.
[5] The resin composition according to [4], wherein the component (A) further contains an epoxy resin liquid at 25 ° C. other than the components (A-2) and (A-1).
[6] The quantitative ratio of the component (A-1) to the component (A-2) (component (A-1): component (A-2)) satisfies the relationship of 1: 0.1 to 1:10. , [5].
[7] The resin composition according to any one of [1] to [6], further containing (D) a thermoplastic resin.
[8] The resin composition according to any one of [1] to [7], which is a resin composition for an insulating layer of a semiconductor chip package.
[9] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [7].
[10] The resin sheet according to [9], which is a resin sheet for an insulating layer of a semiconductor chip package.
[11] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[12] A semiconductor chip package including the circuit board according to [11] and a semiconductor chip mounted on the circuit board.
[13] A semiconductor chip package containing the resin composition according to any one of [1] to [8] or a semiconductor chip sealed with the resin sheet according to [9].

According to the present invention, a resin composition capable of obtaining an insulating layer having excellent shear strength, breaking bending strain, and crackability, and having a low dielectric constant contact and a low relative permittivity; a resin sheet obtained by using the resin composition. , Circuit boards, and semiconductor chip packages can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of the semiconductor chip package (Fan-out type WLP) of the present invention.

Hereinafter, the resin composition, the resin sheet, the circuit board, and the semiconductor chip package of the present invention will be described in detail.

（一般式（１）中、Ｒ¹は、炭素原子数８以上の１価の炭化水素基を表す。） [Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an inorganic filler, and (C) a novolak-type phenol resin containing a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 8 or more carbon atoms.)

By incorporating the component (A), the component (B) and the component (C) into the resin composition, an insulating layer having excellent shear strength, breaking bending strain and crack resistance, and having a low dielectric loss tangent and a low relative permittivity can be obtained. It becomes possible. The resin composition further comprises (D) a thermoplastic resin, (E) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, and a polyisoprene in the molecule, if necessary. It may contain a resin having one or more structures selected from a structure, a polyisobutylene structure, and a polycarbonate structure, (F) a curing agent, (G) a curing accelerator, and (H) a flame retardant.

The “resin component” refers to a component of the non-volatile components constituting the resin composition, excluding (B) the inorganic filler. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
The resin composition contains an epoxy resin. The epoxy resin is not particularly limited as long as it can thermoset the resin composition of the present invention, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule.

The epoxy equivalent of the epoxy resin of the component (A) 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 of the resin composition becomes sufficient, and when the cured product is used as the insulating layer, an insulating layer having a small surface roughness can be obtained. The epoxy equivalent of the component (A) 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 component (A) 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 liquid epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The number average molecular weight of the component (A) is preferably less than 5000, more preferably 4000 or less, still more preferably 3000 or less. The lower limit is preferably 500 or more, more preferably 1000 or more, still more preferably 1500 or more. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

Examples of the epoxy resin include a nitrogen-containing epoxy resin, an epoxy resin having a fused ring structure, a bisphenol AF type epoxy resin, and a fluorine-containing epoxy resin such as a perfluoroalkyl type epoxy resin; bisphenol A type epoxy resin; bisphenol F type epoxy. Resin; Bisphenol S type epoxy resin; Bixilenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naftor novolac type epoxy resin; Epoxy resin; Naftor type epoxy resin; Anthracene type epoxy resin; Glysidylamine type epoxy resin; Glysidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having a butadiene structure; Alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin, phosphorus-containing epoxy resin, etc. However, a nitrogen-containing epoxy resin and an epoxy resin having a fused ring structure are preferable. The epoxy resin may be used alone or in combination of two or more.

The component (A) is preferably (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure from the viewpoint of obtaining an insulating layer having excellent shear strength, breaking bending strain, and crackability.

-(A-1) Nitrogen-containing epoxy resin or epoxy resin having a condensed ring structure-
The component (A) is preferably (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure.

As the nitrogen-containing epoxy resin, a glycidylamine type epoxy resin, an aminophenol type epoxy resin and the like are preferable. Specific examples of the nitrogen-containing epoxy resin include "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and "EP-3950S", "EP-3950L" and "EP-3980S" manufactured by ADEKA. (Glysidylamine type epoxy resin), "GAN", "GOT" (glycidylamine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and the like can be mentioned. These may be used alone or in combination of two or more.

As the epoxy resin having a fused ring structure, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, and a dicyclopentadiene type epoxy resin are preferable. Epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, naphthylene ether-type epoxy resins, and dicyclopentadiene-type epoxy resins are more preferable, and naphthalene-type epoxy resins and naphthol-type epoxy resins are even more preferable. Specific examples of the epoxy resin having a fused ring structure include "HP4032" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalen type tetrafunctional epoxy resin), and "HP-" manufactured by DIC. 7200H ”,“ HP-7200 ”,“ HP-7200L ”, (dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ”( Naphthylene ether type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX8800" ( Anthracene type epoxy resin), Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Examples thereof include "PG-100" and "CG-500" manufactured by Gas Chemical Co., Ltd., and "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These may be used alone or in combination of two or more.

As the component (A-1), a nitrogen-containing epoxy resin and an epoxy resin having a condensed ring structure may be used in combination. When a nitrogen-containing epoxy resin and an epoxy resin having a condensed ring structure are used in combination, their quantitative ratios (nitrogen-containing epoxy resin: epoxy resin having a condensed ring structure) are 1: 0.1 to 1: by mass ratio. A range of 10 is preferred. By setting the amount ratio of the nitrogen-containing epoxy resin to the epoxy resin having a condensed ring structure within such a range, a sufficient heat resistance effect can be obtained. Therefore, from the viewpoint of the effect of sufficient heat resistance, the quantitative ratio of the nitrogen-containing epoxy resin to the epoxy resin having a condensed ring structure (nitrogen-containing epoxy resin: condensed ring structure epoxy resin) is 1: 0. The range of 3 to 1: 5 is more preferable, and the range of 1: 0.6 to 1: 2.5 is even more preferable.

The content of the component (A-1) in the resin composition is preferably 100% by mass when the resin component of the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having excellent shear strength, breaking bending strain, and crackability. Is 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more. The upper limit is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less.

The component (A) further contains an epoxy resin liquid at 25 ° C. other than the components (A-2) and (A-1) in addition to the component (A-1) from the viewpoint of achieving the effect of the present invention. Is preferable. When the component (A-1) is liquid at 25 ° C., the component (A) may not contain the component (A-2).

-Epoxy resin liquid at 25 ° C other than the components (A-2) and (A-1)-
The resin composition may contain (A-2) an epoxy resin that is liquid at 25 ° C. However, the component (A-2) does not include the nitrogen-containing epoxy resin liquid at 25 ° C. and the epoxy resin having a condensed ring structure liquid at 25 ° C. (hereinafter, the component (A-2) is simply referred to as “25”. It is also called "epoxy resin that is liquid at ° C"). The component (A-2) preferably has two or more epoxy groups in one molecule. Further, the component (A-2) preferably has an aromatic structure. The aromatic structure is a chemical structure generally defined as an aromatic, and also includes a polycyclic aromatic and an aromatic heterocycle.

The components (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, and cyclohexane. A dimethanol type epoxy resin and an epoxy resin having a butadiene structure are preferable, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AF type epoxy resin are more preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are further preferable. preferable. Specific examples of the component (A-2) include "828US", "jER828EL" (bisphenol A type epoxy resin), "JER806", "jER807" (bisphenol F type epoxy resin), and "jER152" manufactured by Mitsubishi Chemical Corporation. (Phenol novolak type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy) (Resin), "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. can be mentioned. These may be used alone or in combination of two or more.

When the resin composition contains the component (A-2), the content of the component (A-2) is such that when the resin component in the resin composition is 100% by mass, the crackability and the like are improved. It is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. 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 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and 10% by mass. Below, or 5% by mass or less.

The quantitative ratio of the component (A-1) and the component (A-2) (component (A-1): component (A-2)) has a mass ratio of 1: 0.1 to 1:10. It is preferable to meet. By setting the quantitative ratio of the component (A-1) to the component (A-2) within such a range, it is possible to obtain an insulating layer having excellent shear strength, breaking bending strain, and crackability. From the viewpoint of obtaining such an effect, the quantitative ratio of the component (A-1) to the component (A-2) (component (A-1): component (A-2)) is 1: 0.1 to 1. The range of: 3 is more preferable, and the range of 1: 0.1 to 1: 0.5 is even more preferable.

-(A-3) Other epoxy resins-
The resin composition may contain (A-3) and other epoxy resins in addition to the (A-1) component and the (A-2) component as the (A) component. The component (A-3) is an epoxy resin that does not correspond to any of the components (A-1) and (A-2). The component (A-3) is preferably an epoxy resin having three or more epoxy groups in one molecule and in a solid state at a temperature of 20 ° C. Further, the component (A-3) preferably has an aromatic structure.

As the component (A-3), for example, a cresol novolac type epoxy resin, a trisphenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin are preferable. Specific examples of the component (A-3) include "N-690" (cresol novolac type epoxy resin) manufactured by DIC, "N-695" (cresol novolac type epoxy resin), and "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H "(Trisphenol type epoxy resin)," YX4000HK "(Bixylenol type epoxy resin)," YL7760 "(Bisphenol AF type epoxy resin)," jER1010 "(solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "JER1031S" (tetraphenyl ethane type epoxy resin), "157S70" (bisphenol novolak type epoxy resin), "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

When the resin composition contains the component (A-3), the content of the component (A-3) is preferably 1% by mass or more, more preferably 1% by mass, when the resin component in the resin composition is 100% by mass. Is 5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less. By setting the content of the component (A-3) within such a range, it is possible to obtain an insulating layer exhibiting good mechanical strength and insulation reliability.

<(B) Inorganic filler>
The resin composition contains (B) 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 , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate 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, still more preferably 2 μm or less, from the viewpoint of obtaining an insulating layer having a low surface roughness. 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 "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd. , Tokuyama "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" , "SO-C1" and the like.

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 using 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 alkoxysilane compound, an organosilazane compound, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The content of the inorganic filler in the resin composition is preferably 30% by mass or more, more preferably 30% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. It is 40% by mass or more, more preferably 50% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 90% by mass or less, from the viewpoint of the mechanical strength of the insulating layer, particularly the elongation.

（一般式（１）中、Ｒ¹は、炭素原子数８以上の１価の炭化水素基を表す。） <(C) Novolac-type phenolic resin containing a structural unit represented by the general formula (1)>
The resin composition contains (C) a novolak-type phenol resin containing a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 8 or more carbon atoms.)

The component (C) has a monovalent hydrocarbon group having 8 or more carbon atoms and a long-chain hydrocarbon group. Since it has a long-chain hydrocarbon group, its polarity is lowered, and as a result, it is considered that the dielectric loss tangent and the relative permittivity are lowered, and the compatibility with other resin components is also improved. In addition, having a long-chain hydrocarbon group makes it flexible. It is considered that the insulating layer has low elasticity due to its flexibility, thereby improving the toughness of the resin composition, and as a result, the shear strength, the breaking bending strain, and the crackability are excellent.

The binding site for R ¹ in the general formula (1) and the binding site for the methylene group in the general formula (1) may be any of the ortho-position, the meta-position, and the para-position of phenol. Further, the binding site may be different for each structural unit.

In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 8 or more carbon atoms. R ¹ has 8 or more carbon atoms, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less.

Examples of the monovalent hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The chain hydrocarbon group means a hydrocarbon group composed of only a chain structure and does not contain a cyclic structure in the main chain. However, the chain structure may be linear or branched. The alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon group as a ring structure and not containing an aromatic ring, and the alicyclic hydrocarbon group can be either monocyclic or polycyclic. There may be. However, it does not have to be composed only of an alicyclic hydrocarbon group, and a chain structure may be contained in a part thereof. The aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure. However, it does not have to be composed of only an aromatic ring, and may contain a chain structure or an alicyclic hydrocarbon group as a part thereof, and the aromatic ring may be a monocyclic ring, a polycyclic ring, or a heterocyclic ring. May be.

Examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group and the like. The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

The number of carbon atoms of the alkyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such an alkyl group include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecylic group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group. Can be mentioned.

The number of carbon atoms of the alkenyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such an alkenyl group include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dozesenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadesenyl group and an icosenyl group. Can be mentioned.

The number of carbon atoms of the alkynyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such an alkynyl group include an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecynyl group, a heptadecynyl group, an octadecynyl group, a nonadecinyl group and an icocinyl group. Can be mentioned.
As the chain hydrocarbon group, an alkyl group is preferable.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group and the like, and these may be either monocyclic or polycyclic.

The number of carbon atoms of the cycloalkyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such a cycloalkyl group include a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, a cyclotridecyl group, a cyclotetradecyl group, a cyclopentadecyl group, and a cyclohexadecyl group. Examples thereof include a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, a cycloicosyl group and the like.
And so on.

The number of carbon atoms of the cycloalkenyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such a cycloalkenyl group include a cyclooctenyl group, a cyclononenyl group, a cyclodecenyl group, a cycloundecenyl group, a cyclodozesenyl group, a cyclotridecenyl group, a cyclotetradecenyl group, a cyclopentadecenyl group, and a cyclohexyl group. Examples thereof include a sadesenyl group, a cycloheptadecenyl group, a cyclooctadecenyl group, a cyclononadesenyl group, a cycloicosenyl group and the like.

The number of carbon atoms of the cycloalkynyl group is 8 or more, preferably 10 or more, more preferably 15 or more, still more preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such a cycloalkynyl group include a cyclooctynyl group, a cyclononinyl group, a cyclodecynyl group, a cycloundesynyl group, a cyclododecynyl group, a cyclotridecynyl group, a cyclotetradecynyl group, a cyclopentadecynyl group, and a cyclohexadecynyl group. Examples thereof include a cycloheptadecynyl group, a cyclooctadecynyl group, a cyclononadecinyl group, a cycloicocinyl group and the like.
As the alicyclic hydrocarbon group, a cycloalkyl group is preferable.

The number of carbon atoms of the aromatic hydrocarbon group is 8 or more, preferably 10 or more, more preferably 14 or more, and further preferably 20 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Examples of such an aromatic hydrocarbon group include a naphthyl group and an anthrasenyl group.

A monovalent hydrocarbon group having 8 or more carbon atoms may not have a substituent and 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) OC _1-6 alkyl group, -COOH, -C (O) H, -NO ₂ and the like.

Here, the term "C _pq " (p and q are positive integers and satisfy p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents. 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.

（一般式（２）中、Ｒ²は、水素原子、又は炭素原子数１～７の１価の炭化水素基を表す。） (C) The novolak-type phenolic resin containing the structural unit represented by the general formula (1) may contain two or more different structural units represented by the general formula (1). Further, the component (C) may include a structural unit represented by the general formula (2) as well as a structural unit represented by the general formula (1). The component (C) may contain two or more different structural units represented by the general formula (2).

(In the general formula (2), R ² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms.)

The monovalent hydrocarbon group is as described above, and examples of the monovalent hydrocarbon group having 1 to 7 carbon atoms represented by R ² include an alkyl group, an alkenyl group, and an alkynyl group. can. The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

The alkyl group is preferably an alkyl group having 1 to 7 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms.
The alkenyl group is preferably an alkenyl group having 2 to 7 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and even more preferably an alkenyl group having 2 to 5 carbon atoms.
The alkynyl group is preferably an alkynyl group having 2 to 7 carbon atoms, more preferably an alkynyl group having 2 to 6 carbon atoms, and even more preferably an alkynyl group having 2 to 5 carbon atoms.

Among these, R ² preferably represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.

The monovalent hydrocarbon group having 1 to 7 carbon atoms may not have a substituent and may have a substituent. The substituent is the same as the substituent which may be contained in a monovalent hydrocarbon group having 8 or more carbon atoms represented by R ¹ in the general formula (1).

When the component (C) contains the structural unit represented by the general formula (2), the mass ratio of the structural unit represented by the general formula (1) to the structural unit represented by the general formula (2) ( The mass of the structural unit represented by the general formula (1): the mass of the structural unit represented by the general formula (2) is preferably 1: 0.1 to 5, and more preferably 1: 0.3 to 4. It is preferable, 1: 0.5 to 3 is more preferable.

The content of the component (C) is preferably 1% by mass or more, more preferably 1.5% by mass or more, from the viewpoint of improving crackability and the like when the resin component in the resin composition is 100% by mass. More preferably, it is 2% by mass or more. The upper limit is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 15% by mass or less, more preferably 130% by mass or less, still more preferably 12% by mass or less.

The phenol hydroxyl group equivalent of the component (C) is preferably 50 to 5000, more preferably 50 to 1000, still more preferably 100 to 500, and even more preferably 150 to 300. Within this range, the flexibility of the cured product of the resin composition becomes sufficient, and it is possible to provide an insulating layer having excellent shear strength, breaking bending strain, and crackability, and having a low dielectric loss tangent and a low relative permittivity. The phenol hydroxyl group equivalent of the component (C) can be measured according to JIS K0070, and is the mass of the resin containing 1 equivalent of the phenol hydroxyl group.

The weight average molecular weight of the component (C) is preferably 300 to 10000, more preferably 500 to 8000, and even more preferably 700 to 6000. Here, the weight average molecular weight of the component (C) is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(D) Thermoplastic resin>
The resin composition may contain a thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, and polyester resin. Can be mentioned. The poly (meth) acrylic resin refers to a polyacrylic resin and a polymethacrylic resin.

The polystyrene-equivalent weight average molecular weight of the phenoxy resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the phenoxy resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the phenoxy resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column. Can be calculated by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase and using a standard polystyrene calibration curve. Similarly, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and further in the range of 20,000 to 60,000. preferable.

Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A structure-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. Structure-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YX7180", "YX6954", "YX7553", "YL7769", "YL6774" manufactured by Mitsubishi Chemical Corporation. , "YL7213", "YL7290", "YL7891", "YL7482" and the like. Of these, a phenoxy resin having a polyalkylene oxy structure is preferable, and specific examples thereof include "YX7180" manufactured by Mitsubishi Chemical Corporation.

Specific examples of the polyvinyl acetal resin include, for example, "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", "Electrified Butyral 6000-EP", Sekisui Chemical Co., Ltd. Examples thereof include Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by NEW JAPAN CHEMICAL CO., LTD.

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd., and "KS9100" and "KS9300" manufactured by Hitachi Kasei Co., Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

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

When the resin composition contains the component (D), the content of the component (D) is preferably 1% by mass or more, more preferably 3 when the resin component is 100% by mass from the viewpoint of imparting flexibility. It is mass% or more, more preferably 5% by mass or more, still more preferably 50% by mass or more, 55% by mass or more, and 60% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

<(E) One or more selected from polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule. Resin with structure>
The resin composition contains, as the component (E), a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, and the like. It may contain a resin having one or more structures selected from polycarbonate structures. The component (E) is a resin that is distinguished from the (D) thermoplastic resin.
The component (E) preferably has one or more structures selected from a polybutadiene structure, a poly (meth) acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, or a polycarbonate structure. , Polybutadiene structure, and one or more structures selected from the polycarbonate structure are more preferable. By containing the resin having the above structure, the insulating layer becomes low elasticity, becomes excellent in shear strength, breaking bending strain, and crackability, and further suppresses the occurrence of warpage. In addition, "(meth) acrylate" refers to methacrylate and acrylate. These structures may be contained in the main chain or the side chain.

The component (E) is preferably in a high molecular weight in order to reduce the warp when the resin composition is cured. The number average molecular weight (Mn) is preferably 1,000 or more, more preferably 1500 or more, and further preferably 3000 or more and 5000 or more. The upper limit is preferably 1,000,000 or less, more preferably 900,000 or less. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (E) preferably has a functional group capable of reacting with the component (A) from the viewpoint of improving the mechanical strength of the cured product. The functional group that can react with the component (A) includes a functional group that appears by heating.

In one preferred embodiment, the functional group capable of reacting with the component (A) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. It is a functional group that is more than a species. Among them, as the functional group, a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group are preferable, and a hydroxy group, an acid anhydride group, a phenolic hydroxyl group and an epoxy group are more preferable, and phenol. Phenol is particularly preferred. However, when an epoxy group is contained as a functional group, the number average molecular weight (Mn) is preferably 5,000 or more.

A preferred embodiment of the component (E) is a resin containing a polybutadiene structure, and the polybutadiene structure may be contained in the main chain or the side chain. The polybutadiene structure may be partially or completely hydrogenated. A resin containing a polybutadiene structure is called a polybutadiene resin.

Specific examples of the polybutadiene resin include "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", and "Ricon" manufactured by Clay Valley. 184MA6 "(polybutadiene containing acid anhydride group)," GQ-1000 "(hydroxyl-terminated, carboxyl group-introduced polybutadiene)," G-1000 "," G-2000 "," G-3000 "(both ends) Hydroxyl-terminated polybutadiene), "GI-1000", "GI-2000", "GI-3000" (hydroxyl-terminated polybutadiene with both ends), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX, etc. Can be mentioned. As one embodiment, linear polyimide using hydroxyl group-terminated polybutadiene, diisocyanate compound and tetrabasic acid anhydride as raw materials (polyimide described in JP-A-2006-37083, International Publication No. 2008/153208) and the like can be mentioned. .. The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For the 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.

A preferred embodiment of the component (E) is a resin containing a poly (meth) acrylate structure. A resin containing a poly (meth) acrylate structure is called a poly (meth) acrylic resin.
As poly (meth) acrylic resin, Teisan resin manufactured by Nagase ChemteX, "ME-2000", "W-116.3", "W-197C", "KG-25", "KG-25" manufactured by Negami Kogyo Co., Ltd. KG-3000 ”and the like.

A preferred embodiment of the component (E) is a resin containing a polycarbonate structure. A resin containing a polycarbonate structure is called a polycarbonate resin.
Examples of the polycarbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray. Be done. Further, a linear polyimide made from a hydroxyl 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, more preferably 75% by mass to 85% by mass. The details of the polyimide resin can be referred to in International Publication No. 2016/129541, which is incorporated herein by reference.

Further, as another specific example of the component (E), it is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. Examples of the siloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimides made from tetrabasic acid anhydride (international). Publication No. 2010/053185, JP-A-2002-12667, JP-A-2000-31386, etc.) and the like can be mentioned.

Another specific example of the component (E) is a resin containing an alkylene structure and an alkyleneoxy structure. A resin containing an alkylene structure is referred to as an alkylene resin, and a resin containing an alkyleneoxy structure is referred to as an alkyleneoxy resin. As the polyalkylene oxy structure, a polyalkylene oxy structure having 2 to 15 carbon atoms is preferable, a polyalkylene oxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkylene oxy structure having 5 to 6 carbon atoms is further preferable. Specific examples of the alkylene resin and the alkyleneoxy resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation.

Another specific example of the component (E) is a resin containing an isoprene structure. A resin containing an isoprene structure is called an isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray.

Another specific example of the component (E) is a resin containing an isobutylene structure. A resin containing an isobutylene structure is called an isobutylene resin. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutyrene block copolymer) manufactured by Kaneka Corporation.

When the resin composition contains the component (E), the content of the component (E) is preferably 1% by mass or more, more preferably 3 when the resin component is 100% by mass from the viewpoint of imparting flexibility. It is mass% or more, more preferably 5% by mass or more, still more preferably 50% by mass or more, 55% by mass or more, and 60% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, 15% by mass or less, 10% by mass or less, or 5% by mass or less.

<(F) Curing agent>
The resin composition may further contain (F) 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 (A), and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and cyanate. Examples include ester-based curing agents. The curing agent may be used alone or in combination of two or more. The component (F) 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, and is preferably a phenol-based curing agent and an active ester-based curing agent. It is preferably one or more selected from the agents.

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 conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

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 "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation, "TD-" manufactured by DIC Corporation. 2090, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-" "1163", "KA-1165", "GDP-6115L" manufactured by Gunei Chemical Co., Ltd., "GDP-6115H" and the like can be mentioned.

The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reaction 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, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, 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 structure 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), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" (manufactured by DIC) as an active ester compound containing an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac. Examples of the active ester-based curing agent which is a benzoyl compound of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.

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

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Echilidendiphenyl disyanate, 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 are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which the whole is triazined to become a trimer) and the like can be mentioned.

When the resin composition contains the component (F), the content of the component (F) is preferably 30% by mass or less, more preferably 20% by mass, when the resin component in the resin composition is 100% by mass. Hereinafter, it is more preferably 15% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more.

<(G) Curing accelerator>
The resin composition may contain (G) 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 agents. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator 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. (5,4,0) -Undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -Undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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 trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine 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 Examples thereof include imidazole compounds such as 2-phenylimidazolin and adducts of the imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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, and trimethylguanidine. 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-octadecylviguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allylbiguanide, 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 organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex 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.

When the resin composition contains the component (G), the content of the component (G) is preferably 0.01% by mass to 3% by mass, preferably 0.01% by mass when the resin component of the resin composition is 100% by mass. 03 to 1.5% by mass is more preferable, and 0.05 to 1% by mass is further preferable.

<(H) Flame Retardant>
The resin composition may contain (H) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide and the like. The flame retardant may be used alone or in combination of two or more.

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

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0.5% by mass to 20% by mass. It is preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(I) 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.

<Physical characteristics of resin composition>
The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic of high shear strength. That is, it provides an insulating layer having a high share strength. The share strength is preferably 1.1 kgf / mm ² or more, more preferably 1.3 kgf / mm ² or more, still more preferably 1.5 kgf / mm ² or more, 2 kgf / mm ² or more, 2.5 kgf / mm ² or more. Is. The upper limit of the share strength is not particularly limited, but may be 10 kgf / mm ² or less. The share strength can be measured according to the method described in <Measurement of share strength> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic of high breaking bending strain. That is, it provides an insulating layer having a high breaking bending strain. The breaking bending strain is preferably 1.3% or more, more preferably 1.4% or more, still more preferably 1.5% or more, and 2% or more. The upper limit of the breaking bending strain is not particularly limited, but may be 10% or less. The evaluation of the breaking bending strain can be measured according to the method described in <Measurement of breaking bending strain> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic of being excellent in crackability because it is difficult to crack. That is, it provides an insulating layer having excellent crackability. Specifically, the crackability is excellent to the extent that cracks do not occur unless the cured product is strongly pressed. The crackability can be evaluated according to the method described in <Measurement of crackability> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic of low dielectric loss tangent. That is, it provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.009 or less, still more preferably 0.008 or less, 0.0076 or less. The lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric loss tangent and relative permittivity> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic of low relative permittivity. That is, it provides an insulating layer having a low relative permittivity. The relative permittivity is preferably 5 or less, more preferably 4 or less, still more preferably 3.5 or less. The lower limit of the relative permittivity is not particularly limited, but may be 0.01 or more. The relative permittivity can be measured according to the method described in <Measurement of dielectric loss tangent and relative permittivity> described later.

The resin composition of the present invention can provide an insulating layer having excellent shear strength, breaking bending strain, and crackability, and having a low dielectric loss tangent and a low relative permittivity. Therefore, the resin composition of the present invention comprises a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). A resin composition that can be suitably used as a resin composition for forming (a resin composition for an insulating layer of a circuit board), and a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (a resin composition for forming an interlayer insulating layer). It can be more preferably used as a resin composition for an interlayer insulating layer of a circuit board that forms a conductor layer by plating). It is also suitable as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring). Can be used.

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

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 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, and the like.

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

When a film made of a plastic material is used as a support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyimides. 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, aluminum foil, and the like, 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 support may be matted or corona-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to 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" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumilar T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

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 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. If the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, the resin sheet can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and an interlayer insulating layer on which a conductor layer is formed by plating is formed. Therefore, it can be more preferably used (for an interlayer insulating layer of a circuit board that forms a conductor layer by plating). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (resin sheet for encapsulating a semiconductor chip) or for forming wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring), for example. It can be suitably used for Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP and the like. Further, it can also be suitably used as a MUF (Molding Under Filling) material or the like used after connecting a semiconductor chip to a substrate. In addition, the resin sheet can be suitably used for a wide range of other applications that require high insulation reliability, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

Instead of the resin sheet, 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. 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, and 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 may be in the same range as the resin composition layer in the above-mentioned resin sheet.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing the circuit board of the present invention is as follows.
(1) A 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.
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermally curing the resin sheet to form an insulating layer.
(3) Includes a step of connecting the wiring layers between layers. Further, the method for manufacturing a circuit board may include (4) a step of removing the base material.

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 the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer. It is preferable that the process is at least one of the above steps.

<Process (1)>
The step (1) is a 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. Usually, the base material with a wiring layer has a first metal layer and a second metal layer which are a part of the base material on both sides of the base material, respectively, and is on the side opposite to the surface of the second metal layer on the base material side. It has a wiring layer on the surface. For details, a dry film (photosensitive resist film) is laminated on a substrate and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. A wiring layer is formed by an electrolytic plating method using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off. The first metal layer and the second metal layer may not be provided.

Examples of the substrate include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. A metal layer such as copper foil may be formed on the surface. Further, a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil of Mitsui Metals, trade name "Micro Tin") may be formed on the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. A commercially available product may be used as the dry film.

The laminating conditions of the base material and the dry film are the same as the conditions for laminating the resin sheet in the step (2) described later so as to be embedded in the wiring layer, and the preferable range is also the same.

After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photoresist 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 10/10 μm or less, and further preferably 5 /. It is 5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

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). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. for forming the wiring layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. A nickel alloy, a copper-titanium alloy alloy layer is preferable, a chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or a nickel-chromium alloy alloy layer is more preferable, and a copper single metal layer is preferable. A metal layer is more preferred.

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 to 20 μm. When the step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other in the step (3) is adopted, it is preferable that the thickness of the wiring to be interconnected and the thickness of the wiring not to be connected are different. .. The thickness of the wiring layer can be adjusted by repeating the above-mentioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers is preferably 2 μm or more and 100 μm or less, although it depends on the desired wiring board design. Further, the wiring connected between layers may be convex.

After forming the wiring layer, the dry film is peeled off. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

<Process (2)>
Step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermally curing the resin sheet to form an insulating layer. For details, the wiring layer of the base material with a wiring layer obtained in the above-mentioned step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is thermally cured and insulated. Form a layer.

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

The wiring layer and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. 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 with a pressure of 13 hPa or less.

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

After laminating the resin composition layer on the base material with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature can be in the range of 120 ° C. to 240 ° C. and the curing time can be in the range of 5 minutes to 120 minutes. Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with a wiring layer and heat-cured, or the support may be peeled off before the resin sheet is laminated on the base material with a wiring layer. good. Further, the support may be peeled off before the roughening treatment step described later.

After the resin composition layer is thermally cured to form an insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and polishing may be performed by a known method, and the surface of the insulating layer can be polished using, for example, a surface grinding machine.

<Process (3)>
The step (3) is a step of connecting the wiring layers to each other. The details are a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other. Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other.

When a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other is adopted, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, and mechanical drilling. It is preferably done by. This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that penetrates the support and the insulating layer and exposes the wiring layer.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable step according to a conventional method according to the selected means.

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).

After forming the via hole, a so-called desmear step, which is a smear removing step in the via hole, may be performed. When the conductor layer to be described later is formed by the plating step, the via hole may be subjected to, for example, a wet desmear treatment, and when the conductor layer is formed by the sputtering step, for example, a plasma treatment step may be performed. A dry plasma step may be performed. Further, the desmear step may also serve as a roughening treatment step.

Before forming the conductor layer, the via hole and the insulating layer may be roughened. For the roughening treatment, known procedures and conditions that are usually performed can be adopted. Examples of dry roughening treatment include plasma treatment, and examples of wet roughening treatment include swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. Can be mentioned.

The surface roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, still more preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, still more preferably 600 nm or less. The surface roughness (Ra) can be measured using, for example, a non-contact type surface roughness meter.

After forming the via hole, the conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any conventionally known suitable method such as plating, sputtering, and thin film deposition, and is preferably formed by plating. In one preferred embodiment, the surface of the insulating layer can be plated by, for example, 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. Further, when the support in the resin sheet is a metal leaf, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. 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.

For details, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At that time, along with the formation of the electrolytic plating layer, the via hole may be embedded by electrolytic plating to form a filled via. After forming the electroplating 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. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The conductor layer may include not only linear wiring but also, for example, an electrode pad (land) on which an external terminal can be mounted. Further, the conductor layer may be composed of only the electrode pads.

Further, the conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after forming the plating seed layer, and then performing patterning by etching.

When the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed and the polished or ground surface is used. As long as the surface is horizontal, a conventionally known polishing method or grinding method can be applied. For example, a chemical machine polishing method using a chemical machine polishing device, a machine polishing method such as a buff, or a surface grinding method by rotating a grindstone. And so on. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening treatment step may be performed, or the conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
The step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the circuit board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride. If necessary, the substrate may be peeled off with the conductor layer protected by a protective film.

In other embodiments, the circuit board can be manufactured using the prepreg described above. The manufacturing method is basically the same as when a resin sheet is used.

[Semiconductor chip package]
The first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. A semiconductor chip package can be manufactured by joining a semiconductor chip to the circuit board.

As long as the terminal electrode of the semiconductor chip is connected to the circuit wiring of the circuit board by a conductor, the bonding conditions are not particularly limited, and known conditions used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

A preferred embodiment is to crimp a semiconductor chip to a circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

In addition, another preferred embodiment reflows and joins a semiconductor chip to a circuit board. The reflow condition can be, for example, in the range of 120 ° C to 300 ° C.

After joining the semiconductor chip to the circuit board, for example, the semiconductor chip can be filled with a mold underfill material to obtain a semiconductor chip package. The method of filling with the mold underfill material can be carried out by a known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 as an example. The semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is manufactured from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is rewired on the surface of the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and the side opposite to the side covered by the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and a bump 160 are provided. The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer.
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
It includes (F) a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

<Process (A)>
The step (A) is a step of laminating a temporary fixing film on the base material. The laminating conditions of the base material and the temporary fixing film are the same as the laminating conditions of the wiring layer and the resin sheet in the step (2) in the method of manufacturing the circuit board, and the preferable range is also the same.

The material used for the base material is not particularly limited. As the base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); glass fiber such as FR-4 substrate is impregnated with epoxy resin and the like and heat-cured. Substrate; Examples thereof include a substrate made of a bismaleimidotriazine resin such as BT resin.

The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described later and the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

<Process (B)>
The step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed by using a known device such as a flip chip bonder or a die bonder. The layout and number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, and the like. For example, a matrix having a plurality of rows and a plurality of columns. It can be arranged in a shape and temporarily fixed.

<Process (C)>
In step (C), the resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied onto a semiconductor chip and thermoset to form a sealing layer. Is. In the step (C), it is preferable that the resin composition layer of the resin sheet is laminated on the semiconductor chip and thermally cured to form a sealing layer.

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

Further, the semiconductor chip and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. The laminating conditions in the vacuum laminating method are the same as the laminating conditions of the wiring layer and the resin sheet in the step (2) in the method of manufacturing the circuit board, and the preferable range is also the same.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and heat-cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

The coating conditions for the resin composition are the same as the coating conditions for forming the resin composition layer in the resin sheet of the present invention, and the preferable range is also the same.

<Process (D)>
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. The method of peeling can be appropriately changed depending on the material of the temporary fixing film, for example, a method of heating, foaming (or expanding) the temporary fixing film to peel it off, and irradiating ultraviolet rays from the base material side. Examples thereof include a method of reducing the adhesive strength of the temporary fixing film and peeling it off.

In the method of heating, foaming (or expanding) and peeling off the temporary fixing film, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method of irradiating the substrate side with ultraviolet rays to reduce the adhesive force of the temporary fixing film and peeling it off, the irradiation amount of the ultraviolet rays is usually 10 mJ / cm ² to 1000 mJ / cm ² .

<Process (E)>
The step (E) is a step of forming a rewiring forming layer (insulating layer) on the surface from which the base material of the semiconductor chip and the temporary fixing film have been peeled off.

The material for forming the rewiring forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring forming layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, the material is not particularly limited. Photosensitive resin and thermosetting resin are preferable. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

After forming the rewiring forming layer (insulating layer), via holes may be formed in the rewiring forming layer (insulating layer) in order to interconnect the semiconductor chip and the conductor layer described later.

When the material for forming the rewiring cambium (insulating layer) is a photosensitive resin in forming the via hole, first, the surface of the rewiring cambium (insulating layer) is irradiated with active energy rays through a mask pattern and irradiated. The most wiring layer of the part is photo-cured.

Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed depending on the photosensitive resin. The exposure method includes a contact exposure method in which the mask pattern is exposed in close contact with the rewiring cambium (insulating layer) and an exposure method using parallel light rays without the mask pattern in close contact with the rewiring cambium (insulating layer). Any non-contact exposure method may be used.

Next, the rewiring forming layer (insulating layer) is developed and the unexposed portion is removed to form a via hole. Both wet development and dry development are suitable for development. A known developer can be used as the developer used in wet development.

Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

When the material forming the rewiring forming layer (insulating layer) is a thermosetting resin, the formation of via holes is not particularly limited, and examples thereof include laser irradiation, etching, and mechanical drilling, which may be performed by laser irradiation. preferable. Laser irradiation can be performed using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable step according to a conventional method according to the selected means.

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (diameter of the opening on the surface of the rewiring forming layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more.

<Process (F)>
The step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming the conductor layer on the rewiring forming layer (insulating layer) is the same as the method of forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method of manufacturing the circuit board, which is preferable. The range is similar. The steps (E) and (F) may be repeated, and the conductor layer (rewiring layer) and the rewiring forming layer (insulating layer) may be alternately stacked (build-up).

<Process (G)>
The step (G) is a step of forming a solder resist layer on the conductor layer.

The material for forming the solder resist layer is not particularly limited as long as it has an insulating property at the time of forming the solder resist layer, and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease of manufacturing a semiconductor chip package. .. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

Further, in the step (G), bumping may be performed to form bumps, if necessary. The bumping process can be performed by a known method such as solder balls and solder plating. Further, the formation of the via hole in the bumping process can be performed in the same manner as in the step (E).

<Process (H)>
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them.

The method for dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.

A third aspect of the semiconductor chip package of the present invention is, for example, a rewiring forming layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 as an example. A semiconductor chip package manufactured from the resin composition or resin sheet of the present invention.

[Semiconductor device]
Semiconductor devices to which the semiconductor chip package of the present invention is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example). For example, various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.) can be mentioned.

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.

[Synthesis Example 1: Synthesis of component (E) of Synthesis Example 1]
In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) And Ipsol 150 (aromatic hydrocarbon mixed solvent: Idemitsu). 40 g (manufactured by 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 8 g of isophorone diisocyanate (IPDI, isocyanate group equivalent = 113 g / eq.) Manufactured by Evonik Degussa Japan Co., Ltd. was added while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product was cooled to room temperature, and then 23 g of a cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyl diglycol acetate (manufactured by Daicel) were added thereto. Then, the temperature was raised to 80 ° 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 is regarded as the end point of the reaction, the reaction product is cooled to room temperature, filtered through a 100-mesh filter cloth, and has a butadiene structure and a phenolic hydroxyl group. Hydroxy group-containing butadiene resin: 50% by mass of non-volatile content) was obtained. The number average molecular weight was 5500.

[Synthesis Example 2: Synthesis of component (E) of Synthesis Example 2]
In a flask equipped with a stirrer, a thermometer and a condenser, 292.09 g of ethyldiglycolacetate and 292.09 g of Solbesso 150 (aromatic solvent, manufactured by Exxon Mobile) were charged as solvents, and 100.1 g of diphenylmethane diisocyanate (diphenylmethane diisocyanate). 0.4 mol) and 500.0 g (0.2 mol) of polyisoprene diol (hydroxyl value 46.6 KOH-mg / g, molecular weight 2500) were charged and reacted at 70 ° C. for 4 hours. Then, nonylphenol novolak resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) 195.9 g (0.2 mol) and ethylene glycol bisamhydrotrimericte 41.0 g ( The component (E) (phenolic hydroxyl group-containing butadiene) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group was charged with 0.1 mol), heated to 150 ° C. over 2 hours, and reacted for 12 hours. Resin: non-volatile content 55.2% by mass) was obtained.

[Example 1]
Liquid epoxy resin at 25 ° C (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthalene 20 parts of type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330 g / eq), 10 parts of glycidylamine type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 90 to 105 g / eq), cured. Accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, component (E) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500) 300 parts, aliphatic Modified phenol resin (“ELPC75” manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq, resin containing structural units represented by the general formulas (1) and (2)), SO-C4 ( 950 parts of spherical silica (manufactured by Admatex, average particle size 1 μm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) is mixed, uniformly dispersed with a planetary mixer, and resin. Composition 1 was prepared.

[Example 2]
Liquid epoxy resin at 25 ° C (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 45 parts, synthesized 18 parts of (E) component synthesized in Example 2, 16 parts of bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent of about 185 g / eq), naphthalene type epoxy resin (DIC Co., Ltd. "HP4032", epoxy equivalent) Approximately 144 g / eq) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. "630LSD", epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl- 2-Phenylimidazole) 1 part, active ester-based curing agent (DIC "HPC-8000-65T", active group equivalent of about 225, toluene solution of 65% by mass of non-volatile component) 26.2 parts, aliphatic modified phenol resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) 15 parts, spherical silica surface-treated with SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.)) A resin composition 2 was prepared by mixing 700 parts (with an average particle size of 1 μm) and 50 parts of cyclohexanone manufactured by Matex Co., Ltd. and uniformly dispersing them with a planetary mixer.

[Example 3]
In Example 1, the amount of the aliphatic modified phenol resin (“ELPC75” manufactured by Gun Ei Chemical Industry Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) was changed from 6 parts to 20 parts. A resin composition 3 was produced in the same manner as in Example 1 except for the above items.

[Example 4]
In Example 1, the amount of the aliphatic modified phenol resin (“ELPC75” manufactured by Gun Ei Chemical Industry Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) was changed from 6 parts to 4 parts. A resin composition 4 was prepared in the same manner as in Example 1 except for the above items.

[Example 5]
In Example 1,
1) Change 20 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 330) to 10 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent about 330).
2) 950 parts of spherical silica (manufactured by Admatex, average particle size 1 μm) surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) is subjected to spherical silica A (aminosilane-based cup). Change to 950 parts of spherical silica (average particle size 1.3 μm, specific surface area 7.1 m ² / g) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
3) Further, 300 parts of a phenoxy resin (Mitsubishi Chemical "YX7180BH40", solid content 40%, MEK / cyclohexanone mixed solution) was added.
A resin composition 5 was prepared in the same manner as in Example 1 except for the above items.

[Example 6]
200 parts of component (E) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), 30 parts of phenolphthalene type epoxy resin ("HP4032" manufactured by DIC, epoxy equivalent about 144), liquid epoxy at 25 ° C. Resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, aliphatic modified phenol resin ( "ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) 20 parts, spherical silica (average grain) surface-treated with spherical silica A (aminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.)) Mix 155 parts of diameter 1.3 μm, specific surface area 7.1 m ² / g) and 1 part of curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) and uniformly disperse with a planetary mixer. The resin composition 6 was prepared.

[Example 7]
200 parts of component (E) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), 30 parts of dicyclopentadiene type epoxy resin (“HP7200L” manufactured by DIC, epoxy equivalent about 250), at 25 ° C. Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, aliphatic modified phenol 20 parts of resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq), spherical silica surface-treated with SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.)) 155 parts of Admatex (average particle size 1 μm) and 1 part of curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) are mixed and uniformly dispersed in a planetary mixer to form a resin composition. The thing 7 was made.

[Comparative Example 1]
In Example 1, 6 parts of an aliphatic modified phenol resin (“ELPC75” manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) was used as a cresol novolac resin (“KA-1160” manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent). 117g / eq) 6 parts. A resin composition 8 was produced in the same manner as in Example 1 except for the above items.

[Comparative Example 2]
Liquid epoxy resin at 25 ° C (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 20 parts, bi 20 parts of xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 3 parts of aliphatic modified phenol resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq), accelerated curing 1 part of agent ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 300 parts of (E) component synthesized in Synthesis Example 2, SO-C4 (aminosilane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd.) 950 parts of spherical silica (manufactured by Admatex Co., Ltd., average particle size 1 μm) surface-treated with “KBM573”) was mixed and uniformly dispersed with a planetary mixer to prepare a resin composition 9.

[Comparative Example 3]
In Example 2,
1) 16 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent about 185 g / eq), 20 parts of naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent about 330 g / eq) To
2) 15 parts of an aliphatic modified phenol resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq), a phenoxy resin ("YX7180BH40" manufactured by Mitsubishi Chemical Co., Ltd., solid content 40%, MEK / cyclohexanone mixed solution) ) Changed to 40 copies.
A resin composition 10 was prepared in the same manner as in Example 2 except for the above items.

<Measurement of share strength>
The resin compositions prepared in Examples and Comparative Examples were filled on a silicon wafer coated with polyimide on a cylinder having a height of 5 mm using a silicon rubber frame hollowed out to a diameter of 4 mm. After heating at 180 ° C. for 90 minutes, a test piece was prepared by removing the silicon rubber frame. The share strength of the interface between the polyimide and the test piece was measured with a bond tester (Series 4000 manufactured by Dage) under the conditions that the head position was 1 mm from the substrate and the head speed was 700 μm / s. The test was carried out 5 times and the average value was used.

<Measurement of breaking bending strain>
The resin compositions produced in Examples and Comparative Examples were compression-molded on a release-treated SUS plate with a compression molding device so as to have a thickness of 300 μm under the condition of 120 ° C. Then, the resin composition was peeled off from the SUS plate and heat-cured under the conditions of 180 ° C. for 90 minutes to obtain a test piece for measuring breaking bending strain. The breaking bending strain (%) at 23 ° C. was determined using a tensile tester "RTC-1250A" manufactured by Orientec. The test was carried out 5 times and the average value was used.

<Measurement of crackability>
The resin compositions produced in Examples and Comparative Examples were compression-molded on a mold-released SUS plate with a compression molding device so as to have a thickness of 100 μm under the condition of 120 ° C. Then, the resin composition was peeled off from the SUS plate and heat-cured under the conditions of 180 ° C. for 90 minutes to obtain a test piece for confirming crackability, which was evaluated according to the following evaluation criteria.
[Evaluation criteria]
⊚: No cracks occur even when pressed strongly.
◯: No crack occurs even if pressed lightly.
Δ: When pressed strongly, cracks occur.
×: When pressed lightly, cracks occur.

<Measurement of dielectric loss tangent and relative permittivity>
The resin compositions produced in Examples and Comparative Examples were compression-molded on a mold-released SUS plate using a compression molding device at 120 ° C. to a thickness of 200 μm. After that, the resin composition was peeled off from the SUS plate and heat-cured under the conditions of 180 ° C. for 90 minutes, and the cured product was cut into a length of 80 mm and a width of 2 mm, which was used as an evaluation sample. This evaluation sample was measured for a relative permittivity at a measurement frequency of 5.8 GHz and a dielectric loss tangent at a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP8632B device manufactured by Agilent Technologies.

The components used for preparing the resin compositions of Examples and Comparative Examples and their blending amounts (parts by mass) are shown in the table below. The abbreviations in the table below are as follows.
Content of component (C) (% by mass): Content of component (C) when the resin component is 100% by mass.

In each example, it has been confirmed that even when the components (D) to (G) are not contained, the same result as in the above-mentioned example is obtained, although the degree is different.

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulating layer 130 Rewiring forming layer (insulating layer)
140 Conductor layer (rewiring layer)
150 solder resist layer 160 bumps

Claims (12)

(A) Epoxy resin,
It contains (B) an inorganic filler and (C) a novolak-type phenolic resin containing a structural unit represented by the following general formula (1) .
A resin composition in which the component (A) contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure .

(In the general formula (1), R ¹ represents a monovalent hydrocarbon group having 8 or more carbon atoms.) The resin composition according to claim 1, wherein the content of the component (B) is 30% by mass or more and 95% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 1% by mass or more and 15% by mass or less when the content of the resin component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein the component (A) further contains an epoxy resin liquid at 25 ° C. other than the components (A-2) and (A-1). Claimed that the quantitative ratio of the component (A-1) to the component (A-2) (component (A-1): component (A-2)) satisfies the relationship of 1: 0.1 to 1:10. 4. The resin composition according to 4. The resin composition according to any one of claims 1 to 5 , further comprising (D) a thermoplastic resin. The resin composition according to any one of claims 1 to 6 , which is a resin composition for an insulating layer of a semiconductor chip package. 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 6 . The resin sheet according to claim 8 , which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor chip package including the circuit board according to claim 10 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising the resin composition according to any one of claims 1 to 7 or a semiconductor chip sealed with the resin sheet according to claim 8 .

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