JP2018145409A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a resin composition that can provide an insulator layer in which the shear strength, breaking flexural strain and crack resistance are excellent and the dielectric loss tangent and relative permittivity are low; and a resin sheet, a circuit board, and a semiconductor chip package that are obtained using the resin composition.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an inorganic filler, and (C) a novolac type phenolic resin comprising a structural unit represented by the general formula (1) in the figure, where Rrepresents a monovalent hydrocarbon group having 8 or more carbon atoms.SELECTED DRAWING: None

Description

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

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in semiconductor package substrates, build-up layers have been multilayered, and miniaturization and higher density of wiring have been demanded. Furthermore, with the widespread use of smartphones and tablet PCs, there is an increasing demand for thinning, and there is a need for thin package substrates such as a thin core material and a coreless structure. These materials are required to have characteristics such as a low thermal expansion coefficient. In order to obtain a low thermal expansion coefficient, the resin composition used to form the insulating layer used for these materials has been studied to contain a large amount of inorganic filler. In the resin composition to be contained, since the cured body of the resin composition becomes brittle, when the package substrate is handled, problems such as occurrence of a resin chip of the cured body from the end portion may occur.

  For example, in Patent Document 1, a thermosetting resin composition containing a phenol-based curing agent or the like provides a resin composition that can prevent resin chipping even though the coefficient of linear thermal expansion is low.

JP 2014-15608 A

  The present invention provides a resin composition suitable for forming an insulating layer used in a build-up layer, a wafer level chip size package or the like of a wiring board that has been densified, thinned, or coreless. Yes, specifically, a resin composition that is excellent in shear strength, bending bending strain, and crack resistance, and can obtain an insulating layer having a low dielectric loss tangent and relative dielectric constant; obtained using the resin composition, The object is to provide a resin sheet, a circuit board, and a semiconductor chip package.

  As a result of intensive studies to solve the above problems, the present inventors have incorporated a resin composition with an epoxy resin, an inorganic filler, and a predetermined novolac-type phenol resin, so that the shear strength, fracture bending strain, and resistance to resistance are increased. The inventors have found that an insulating layer having excellent cracking property and low dielectric loss tangent and relative dielectric constant can be obtained, and the present invention has been completed.

（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 comprising (B) an inorganic filler, and (C) a novolac-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.)
[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 nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], in which the content of the component (C) is 1% by mass to 15% by mass when 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 that is liquid at 25 ° C. other than the components (A-2) and (A-1).
[6] The quantity ratio of the component (A-1) to the component (A-2) (the component (A-1): the component (A-2)) satisfies the relationship of 1: 0.1 to 1:10. [5] The resin composition according to [5].
[7] The resin composition according to any one of [1] to [6], further comprising (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 including 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 comprising the circuit board according to [11] and a semiconductor chip mounted on the circuit board.
[13] A semiconductor chip package including a semiconductor chip sealed with the resin composition according to any one of [1] to [8] or the resin sheet according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the insulating layer which is excellent in a shear strength, a fracture | rupture bending strain, and a crackability, and whose dielectric loss tangent and a dielectric constant are low; Resin sheet obtained using this resin composition A circuit board and a semiconductor chip package can be provided.

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

  Hereinafter, the resin composition, resin sheet, circuit board, and 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 novolac 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 including the component (A), the component (B) and the component (C) in the resin composition, an insulating layer having excellent shear strength, breaking bending strain, and crack resistance, and having a low dielectric loss tangent and relative dielectric constant is obtained. It becomes possible. If necessary, the resin composition may further comprise (D) a thermoplastic resin, (E) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene in the molecule. 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 may be included.

  The “resin component” refers to a component excluding (B) the inorganic filler among the non-volatile components constituting the resin composition. 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 thermally cure the resin composition of the present invention, but preferably contains an epoxy resin having two or more epoxy groups in one molecule.

  The epoxy equivalent of the epoxy resin as 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. By becoming this range, the crosslinked density of the hardened | cured material of a resin composition becomes enough, and when using hardened | cured material as an insulating layer, an insulating layer with small surface roughness can be brought about. In addition, the epoxy equivalent of (A) component can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of epoxy groups.

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

  (A) The number average molecular weight of a component becomes like this. Preferably it is less than 5000, More preferably, it is 4000 or less, More preferably, it is 3000 or less. The lower limit is preferably 500 or more, more preferably 1000 or more, and further 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 fluorine-containing epoxy resins such as nitrogen-containing epoxy resins, epoxy resins having a condensed ring structure, bisphenol AF type epoxy resins, and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy Resin; Bisphenol S type epoxy resin; Bixylenol type epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naphthol novolac type epoxy resin; Phenol novolac type epoxy resin; Tert-butyl-catechol type epoxy resin; Epoxy resin; Naphthol type epoxy resin; Anthracene type epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy Bi-resin type epoxy resin; Linear aliphatic epoxy resin; Epoxy resin having butadiene structure; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring-containing epoxy resin; Cyclohexane dimethanol type epoxy resin; Type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin, phosphorus-containing epoxy resin, and the like. Nitrogen-containing epoxy resins and epoxy resins having a condensed ring structure are preferable. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 excellent in shear strength, breaking bending strain, and crackability.

-(A-1) a nitrogen-containing epoxy resin or an 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, glycidylamine type epoxy resin, 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, “EP-3950S”, “EP-3950L”, and “EP-3980S” manufactured by ADEKA. "(Glycidylamine type epoxy resin)", Nippon Kayaku Co., Ltd. "GAN", "GOT" (glycidylamine type epoxy resin), and the like. These may be used alone or in combination of two or more.

  As the epoxy resin having a condensed ring structure, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, dicyclopentadiene type epoxy resin are preferable, and naphthalene type An epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, a naphthylene ether type epoxy resin, and a dicyclopentadiene type epoxy resin are more preferable, and a naphthalene type epoxy resin and a naphthol type epoxy resin are more preferable. Specific examples of the epoxy resin having a condensed ring structure include “HP4032” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene 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 novolak type epoxy resin), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX8800" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Anthracene type epoxy resin) “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Company, “YL7800” (fluorene type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “ Examples thereof include “PG-100”, “CG-500”, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation. 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 the nitrogen-containing epoxy resin and the epoxy resin having a condensed ring structure are used in combination, the quantitative ratio (nitrogen-containing epoxy resin: epoxy resin having a condensed ring structure) is 1: 0.1 to 1: A range of 10 is preferred. By setting the amount ratio of the nitrogen-containing epoxy resin and 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 sufficient heat resistance, the mass ratio of the nitrogen-containing epoxy resin and 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 more preferable.

  The content of the component (A-1) in the resin composition is preferably when the resin component of the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer excellent in shear strength, breaking bending strain, and crackability. Is 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Although an upper limit is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

  The component (A) further contains a liquid epoxy resin at 25 ° C. other than the components (A-2) and (A-1) together with the component (A-1) from the viewpoint of achieving the effects of the present invention. It is preferable. When the component (A-1) is liquid at 25 ° C., the component (A) may not contain the component (A-2).

-(A-2) Epoxy resin that is liquid at 25 ° C other than (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 a nitrogen-containing epoxy resin that is liquid at 25 ° C. and an epoxy resin that has a condensed ring structure that is liquid at 25 ° C. (hereinafter, the component (A-2) is simply referred to as “25 Sometimes referred to as an epoxy resin that is liquid at ℃.) The component (A-2) preferably has two or more epoxy groups in one molecule. Moreover, it is preferable that (A-2) component has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

  As the component (A-2), 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, cyclohexane A dimethanol type epoxy resin and an epoxy resin having a butadiene structure are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AF type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable. preferable. Specific examples of the component (A-2) include “828US”, “jER828EL” (bisphenol A type epoxy resin), “JER806”, “jER807” (bisphenol F type epoxy resin), “jER152” manufactured by Mitsubishi Chemical Corporation. (Phenol novolac type epoxy resin), “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “EX-721” (glycidyl ester type epoxy manufactured by Nagase ChemteX Corporation) Resin), “Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. These may be used alone or in combination of two or more.

  When the resin composition contains the component (A-2), when the content of the component (A-2) is 100% by mass of the resin component in the resin composition, from the viewpoint of improving crackability and the like, Preferably it is 1 mass% or more, More preferably, it is 2 mass% or more, More preferably, it is 3 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, and further preferably 20% by mass or less, 10% by mass. Or 5% by mass or less.

  The quantity ratio of the component (A-1) and the component (A-2) (the component (A-1): the component (A-2)) is a mass ratio and has a relationship of 1: 0.1 to 1:10. It is preferable to satisfy. By setting the quantity 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: 0.1-1 : 3 is more preferable, and a range of 1: 0.1 to 1: 0.5 is more preferable.

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

  As a preferable 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 novolak type epoxy resin), “N-695” (cresol novolak type epoxy resin) manufactured by DIC, “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” (tetraphenylethane type epoxy resin), “157S70” (bisphenol novolac type epoxy resin), “jER1031S” (tetraphenylethane 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 100% 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. An upper limit becomes like this. Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less. By setting the content of the component (A-3) within such a range, an insulating layer exhibiting good mechanical strength and insulation reliability can be obtained.

<(B) Inorganic filler>
The resin composition contains (B) an inorganic filler. The material of the inorganic filler is not particularly limited. 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, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, and more preferably 2 μm or less from the viewpoint of obtaining an insulating layer having a low surface roughness. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. Examples of commercially available inorganic fillers having such an average particle diameter include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, and “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Corporation, "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" manufactured by Admatechs And “SO-C1”.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat 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., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The content of the inorganic filler in the resin composition is preferably 30% by mass or more, more preferably, when the nonvolatile 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 mass% or more, More preferably, it is 50 mass% or more. The upper limit is preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 90% by mass or less, from the viewpoint of mechanical strength of the insulating layer, particularly 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 Structural Unit Represented by General Formula (1)>
The resin composition contains (C) a novolac 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, the polarity is lowered, and as a result, the dielectric loss tangent and the relative dielectric constant are lowered, and the compatibility with other resin components is also improved. Moreover, it comes to show a flexibility by having a long-chain hydrocarbon group. Since it exhibits flexibility, the insulating layer has low elasticity, which improves the toughness of the resin composition. As a result, it is considered that the shear strength, fracture bending strain, and crackability are improved.

The bonding site of R ^{1 in} the general formula (1) and the bonding site of the methylene group in the general formula (1) may be any of the ortho position, the meta position, and the para position of the 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 still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 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 only of a chain structure, and the main chain does not include a cyclic structure. 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. The alicyclic hydrocarbon group may be monocyclic or polycyclic. There may be. However, it is not necessary to be composed only of an alicyclic hydrocarbon group, and a part thereof may include a chain structure. An aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure. However, it is not necessary to be composed only of an aromatic ring, and a part thereof may contain a chain structure or an alicyclic hydrocarbon group, and the aromatic ring may be any of monocyclic, polycyclic and heterocyclic rings. It may be.

  Examples of the chain hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The alkyl group, alkenyl group, and alkynyl group may be either 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 still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such alkyl groups include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and the like. 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 still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such alkenyl groups include octenyl, nonenyl, decenyl, undecenyl, dozecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, etc. Can be mentioned.

The number of carbon atoms in the alkynyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such alkynyl groups include octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, icosinyl, etc. 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 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 still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such cycloalkyl groups include cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, A cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, a cycloicosyl group, etc. are mentioned.
Etc.

  The number of carbon atoms of the cycloalkenyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such a cycloalkenyl group include a cyclooctenyl group, a cyclononenyl group, a cyclodecenyl group, a cycloundecenyl group, a cyclododecenyl group, a cyclotridecenyl group, a cyclotetradecenyl group, a cyclopentadecenyl group, a cyclohexenyl group, and the like. Examples include a sadecenyl group, a cycloheptadecenyl group, a cyclooctadecenyl group, a cyclononadecenyl group, and a cycloicosenyl group.

The number of carbon atoms of the cycloalkynyl group is 8 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such a cycloalkynyl group include a cyclooctynyl group, a cyclononinyl group, a cyclodecynyl group, a cycloundecynyl group, a cyclododecynyl group, a cyclotridecynyl group, a cyclotetradecynyl group, a cyclopentadecynyl group, a cyclohexadecynyl group, Examples include a cycloheptadecynyl group, a cyclooctadecynyl group, a cyclononadecynyl group, a cycloicosinyl 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 still more preferably 20 or more. Although an upper limit is not specifically limited, Preferably it is 50 or less, More preferably, it is 40 or less, More preferably, it is 30 or less. Examples of such aromatic hydrocarbon groups include a naphthyl group and an anthracenyl group.

The 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, for example, a halogen atom, -OH, -O-C _1-6 alkyl group, -N (C _1-6 alkyl) _2, C _1-6 alkyl, C _{6- A 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like.

Here, the term “C _pq ” (p and q are positive integers and satisfies 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” refers to an alkyl group having 1 to 6 carbon atoms.

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

（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 novolac type phenol 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). Moreover, (C) component may contain the structural unit represented by General formula (2) with the structural unit represented by General formula (1). In addition, (C) component may contain the structural unit represented by 2 or more types of different general formula (2).

(In 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. it can. The alkyl group, alkenyl group, and alkynyl group may be either 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 still 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 further 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 further 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 the monovalent hydrocarbon group having 8 or more carbon atoms represented by R ¹ in the general formula (1) may have.

  When the component (C) includes the structural unit represented by the general formula (2), the mass ratio of the structural unit represented by the general formula (1) and 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, more preferably 1: 0.3 to 4. Preferably, 1: 0.5-3 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 mass% or more. Although an upper limit is not specifically limited as long as the effect of this invention is show | played, Preferably it is 15 mass% or less, More preferably, it is 130 mass% or less, More preferably, it is 12 mass% or less.

  The phenol hydroxyl group equivalent of (C) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-1000, More preferably, it is 100-500, More preferably, it is 150-300. By being in this range, the flexibility of the cured product of the resin composition becomes sufficient, and an insulating layer having excellent shear strength, breaking bending strain, and cracking property, and having a low dielectric loss tangent and relative dielectric constant can be provided. In addition, the phenol hydroxyl group equivalent of (C) component can be measured according to JISK0070, and is the mass of resin containing 1 equivalent phenol hydroxyl group.

  The weight average molecular weight of (C) component becomes like this. Preferably it is 300-10000, More preferably, it is 500-8000, More preferably, it is 700-6000. 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, polyester resin. Is mentioned. Poly (meth) acrylic resin refers to polyacrylic resin and polymethacrylic resin.

  The weight average molecular weight in terms of polystyrene 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 still 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 KK as a column. Can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase. 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” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX7180”, “YX6954”, “YX7553”, “YL7769”, “YL6794” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ”,“ YL7213 ”,“ YL7290 ”,“ YL7891 ”,“ YL7482 ”, and the like. Of these, a phenoxy resin having a polyalkyleneoxy structure is preferable, and specific examples thereof include “YX7180” manufactured by Mitsubishi Chemical Corporation.

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

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.

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

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “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 at least 5 mass%, more preferably at least 5 mass%, even more preferably at least 50 mass%, at least 55 mass%, at least 60 mass%. An upper limit becomes like this. Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less.

<(E) One or more kinds selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule Resin having structure>
The resin composition has, as (E) component, (E) in the molecule, polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and 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 thermoplastic resin (D).
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. It is more preferable to have one or more structures selected from a polybutadiene structure and a polycarbonate structure. By including the resin having the above structure, the insulating layer has low elasticity, becomes excellent in shear strength, breaking bending strain, and crackability, and further suppresses the occurrence of warpage. “(Meth) acrylate” refers to methacrylate and acrylate. These structures may be contained in the main chain or in the side chain.

  The component (E) preferably has 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. In addition, as a functional group which can react with (A) component, the functional group which appears by heating shall also be included.

  In a 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 of more than species. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A functional hydroxyl group is particularly preferred. However, when an epoxy group is included 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 in the side chain. Note that part or all of the polybutadiene structure may be hydrogenated. A resin containing a polybutadiene structure is referred to as a polybutadiene resin.

  Specific examples of the polybutadiene resin include “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5”, “Ricon 131MA10”, “Ricon 131MA17”, “Ricon 131MA20”, “Ricon” manufactured by Clay Valley. 184MA6 "(acid anhydride group-containing polybutadiene)," GQ-1000 "(hydroxyl group, carboxyl group-introduced polybutadiene) manufactured by Nippon Soda Co., Ltd.," G-1000 "," G-2000 "," G-3000 "(both ends) Hydroxyl group polybutadiene), “GI-1000”, “GI-2000”, “GI-3000” (hydroxylated hydrogenated polybutadiene at both ends), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy manufactured by Nagase ChemteX) Resin) and the like. As one embodiment, linear polyimide (polyimide described in JP 2006-37083 A and WO 2008/153208 A) using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as a raw material can be used. . The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the descriptions in JP-A-2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated herein.

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 referred to as a poly (meth) acrylic resin.
Examples of the poly (meth) acrylic resin include Teissan resin manufactured by Nagase ChemteX Corporation, “ME-2000”, “W-116.3”, “W-197C”, “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”, “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, “C-1090”, “C-2090”, “C-3090” (polycarbonate diol) manufactured by Kuraray. It is done. A linear polyimide made from hydroxyl group-terminated polycarbonate, diisocyanate compound and tetrabasic acid anhydride can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the description of International Publication No. 2016/129541, the contents of which are incorporated herein.

  Another specific example of the component (E) is a resin containing a siloxane structure. A resin containing a siloxane structure is called a siloxane resin. As the siloxane resin, for example, “SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimide made from amine group-terminated polysiloxane and tetrabasic acid anhydride (International JP 2010/053185 A, JP 2002-12667 A and JP 2000-319386 A).

  Another specific example of the component (E) is a resin containing an alkylene structure or an alkyleneoxy structure. A resin containing an alkylene structure is called an alkylene resin, and a resin containing an alkyleneoxy structure is called an alkyleneoxy resin. The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and further preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. Specific examples of the alkylene resin and alkyleneoxy resin include “PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers.

  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 Co., Ltd.

  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-isobutylene diblock 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 at least 5 mass%, more preferably at least 5 mass%, even more preferably at least 50 mass%, at least 55 mass%, at least 60 mass%. An upper limit becomes like this. Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less, 15 mass% or less, 10 mass% or less, or 5 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 component (A). For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate. Examples include ester-based curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (F) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent, a phenol curing agent, and an active ester curing It is preferable that it is 1 or more types selected from an agent.

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

  Specific examples of the phenol-based curing agent and naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. ”,“ GPH ”,“ SN170 ”,“ SN180 ”,“ SN190 ”,“ SN475 ”,“ SN485 ”,“ SN495V ”,“ SN375 ”,“ SN395 ”manufactured by Nippon Steel & Sumitomo Metal,“ TD- ”manufactured by DIC 2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "," EXB-9500 "," HPC-9500 "," KA-1160 "," KA- " 1163 "," KA-1165 "," GDP-6115L "," GDP-6115H "manufactured by Gunei Chemical Co., Ltd., and the like.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester 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, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  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 a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "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 "as an active ester compound containing an acetylated product of phenol novolac ( Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated product of phenol novolac, "YLH1026" as an active ester-based curing agent is benzoyl product of E Nord novolac (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 Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

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

  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. Further, 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 a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

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

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

  When the resin composition contains the component (G), the content of the component (G) is preferably 0.01% by mass to 3% by mass when the resin component of the resin composition is 100% by mass. 03-1.5 mass% is more preferable, and 0.05-1 mass% is further more 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, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, such as “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but preferably 0.5% by mass to 20% by mass when the nonvolatile component in the resin composition is 100% by mass. Preferably 0.5 mass%-15 mass%, More preferably, 0.5 mass%-10 mass% are further more preferable.

<(I) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, In addition, binders, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and resin additives such as colorants can be used.

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

  A cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a property of high fracture bending strain. That is, an insulating layer having a high breaking bending strain is provided. The breaking bending strain is preferably 1.3% or more, more preferably 1.4% or more, and further 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 performed according to the method described in <Measurement of breaking bending strain> described later.

  A cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 90 minutes exhibits the property of being excellent in cracking properties because it is difficult to crack. That is, an insulating layer having excellent cracking properties is provided. Specifically, the cracking property is excellent to the extent that cracks do not occur unless the cured product is pressed strongly. The evaluation of crackability can be performed according to the method described in <Measurement of crackability> described later.

  A cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic of low dielectric loss tangent. That is, an insulating layer having a low dielectric loss tangent is provided. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.009 or less, still more preferably 0.008 or less and 0.0076 or less. The lower limit value 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 later in <Measurement of dielectric loss tangent and relative dielectric constant>.

  A cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes exhibits a characteristic that the relative dielectric constant is low. That is, an insulating layer having a low relative dielectric constant is provided. The relative dielectric constant is preferably 5 or less, more preferably 4 or less, and still more preferably 3.5 or less. The lower limit value of the relative dielectric constant 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 relative dielectric constant. Therefore, the resin composition of the present invention comprises a resin composition (resin composition for an insulating layer of a semiconductor chip package) for forming an insulating layer of a semiconductor chip package, and an insulating layer of a circuit board (including a printed wiring board). Resin composition for forming an interlayer insulating layer that can be suitably used as a resin composition for forming (resin composition for an insulating layer of a circuit board) and on which a conductor layer is formed by plating ( The resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating can be used more suitably. Also suitable as a resin composition for sealing a semiconductor chip (resin composition for sealing 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 formed on the support and formed of the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less from the viewpoint of thinning. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

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

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

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

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

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

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

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

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

  The resin sheet can be suitably used for sealing a semiconductor chip (resin sheet for sealing a semiconductor chip) or forming a wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring). 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. Moreover, it can be used suitably also for the MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board | substrate. Further, the resin sheet can be suitably used for forming a wide range of other applications requiring high insulation reliability, for example, an insulating layer of a circuit board such as a printed wiring board.

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

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

[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 includes:
(1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer and thermally curing to form an insulating layer;
(3) including a step of interconnecting the wiring layers. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.

  The step (3) is not particularly limited as long as the wiring layers can be connected to each other, but 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 it is at least one of these steps.

<Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate. Usually, the base material with a wiring layer has a first metal layer and a second metal layer which are part of the base material on both surfaces of the base material, respectively, and is opposite to the base material side surface of the second metal layer. A wiring layer is provided on the surface. In detail, a dry film (photosensitive resist film) is laminated on a substrate, and a pattern dry film is formed by exposing and developing under a predetermined condition using a photomask. A wiring layer is formed by electrolytic plating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off. Note that the first metal layer and the second metal layer may not be provided.

  Examples of the base material include glass epoxy substrates, metal substrates (such as stainless steel and cold rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. A metal layer such as a copper foil may be formed on the surface. Further, a metal layer such as a first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil, trade name “Micro Thin”) that can be peeled off 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 commercial product may be used as the dry film.

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

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

  The line (circuit width) / space (inter-circuit width) 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 even more 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 need not 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 dry film pattern, a wiring layer is formed, and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern 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. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The thickness of the wiring layer 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, although it depends on the desired wiring board design. In the step (3), 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, it is preferable that the wiring of the interlayer connection and the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Of each wiring layer, the thickness of the thickest wiring layer (conductive pillar) depends on the design of the desired wiring board, but is preferably 2 μm or more and 100 μm or less. Further, the wiring for interlayer connection may be convex.

  After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed using, for example, an alkaline peeling 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.

<Step (2)>
Step (2) is a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting to form an insulating layer. For details, the wiring layer of the substrate 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 to be insulated. Form a layer.

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

  Lamination of the wiring layer and the resin sheet may be performed by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

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

  After laminating the resin composition layer on the substrate 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, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, 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 for the resin sheet may be peeled after the resin sheet is laminated on the substrate with the wiring layer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. Good. Moreover, you may peel a support body before the roughening process process mentioned 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 may be polished by a known method. For example, the surface of the insulating layer can be polished using a surface grinder.

<Step (3)>
Step (3) is a step of interconnecting the wiring layers. More specifically, this is a step of forming via holes in the insulating layer, forming a conductor layer, and interconnecting the wiring layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers.

  When adopting a process of forming a via hole in the insulating layer, forming a conductor layer and interconnecting the wiring layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. can be mentioned, but laser irradiation Is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using 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 exposes the wiring layer through the support and the insulating layer.

  The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the outline 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 process, which is a smear removing process in the via hole, may be performed. When the conductor layer described later is formed by a plating process, the via hole may be subjected to, for example, a wet desmear process, and when the conductor layer is formed by a sputtering process, for example, a plasma treatment process or the like. A dry desmear process may be performed. Moreover, the desmear process may serve as the roughening process.

  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 employed. Examples of dry roughening treatment include plasma treatment, etc., and examples of wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. Is 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, and further preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and 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, a conductor layer is formed. The conductor material which comprises a conductor layer is not specifically limited, A conductor layer can be formed by arbitrary well-known methods, such as plating, a sputter | spatter, vapor deposition, and it is preferable to form by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Moreover, when the support body in a resin sheet is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method. The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

  Specifically, 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 on the exposed plating seed layer by electrolytic plating. At that time, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as the said dry film.

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

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

  When adopting a process of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers, the insulating layer polishing method or grinding method can be used to expose the wiring layer, polishing or grinding surface If it is horizontal, it will not specifically limit, A conventionally well-known grinding | polishing method or grinding method can be applied, for example, the chemical mechanical polishing method by a chemical mechanical polishing apparatus, the mechanical polishing methods, such as a buff, The surface grinding method by grindstone rotation Etc. Similar to the step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening step may be performed, or a 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)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution. As needed, you may peel a base material in the state which protected the conductor layer with the 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 using a resin sheet.

[Semiconductor chip package]
A 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 bonding a semiconductor chip to the circuit board.

  As long as the terminal electrode of the semiconductor chip is conductively connected to the circuit wiring of the circuit board, the joining condition is not particularly limited, and a known condition used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.

  In a preferred embodiment, the semiconductor chip is pressure-bonded to the 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 another preferred embodiment, the semiconductor chip is reflowed and bonded to the circuit board. As reflow conditions, it can be set as the range of 120 to 300 degreeC, for example.

  After the semiconductor chip is bonded to the circuit board, for example, the semiconductor chip package can be obtained by filling the semiconductor chip with a mold underfill material. The method of filling with the mold underfill material can be performed 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. A semiconductor chip package (Fan-out WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which a sealing layer 120 is manufactured using the resin composition or resin sheet of the present invention. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and a rewiring formed on a surface opposite to the side covered with the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (redistribution layer) 140, a solder resist layer 150, and bumps 160 are provided. A manufacturing method of such a semiconductor chip package is as follows:
(A) Laminating a temporary fixing film on a substrate;
(B) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(C) The 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 it to form a sealing layer;
(D) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(E) forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip substrate and the temporarily fixed film peeled off;
(F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. In addition, 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 dividing them into individual pieces.

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

  The material used for the substrate is not particularly limited. As a base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); thermosetting treatment by impregnating glass fiber such as FR-4 substrate with epoxy resin. And a substrate made of bismaleimide triazine resin such as BT resin.

  The material for the temporarily 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)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a known apparatus such as a flip chip bonder or a die bonder. The layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like, for example, a matrix having a plurality of rows and a plurality of columns. Can be aligned and fixed temporarily.

<Process (C)>
Step (C) is 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 thermally curing to form a sealing layer. It 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 the sealing layer.

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

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

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

  The application conditions for the resin composition are the same as the application conditions for forming the resin composition layer in the resin sheet of the present invention, and the preferred ranges are also the same.

<Process (D)>
A process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip. The method of peeling can be appropriately changed according to the material of the temporarily fixed film, for example, the method of heating, foaming (or expanding) the temporarily fixed film and peeling, and irradiating ultraviolet rays from the substrate side, Examples include a method of reducing the pressure-sensitive adhesive strength of the temporarily fixed film and peeling it off.

In the method of peeling by heating and foaming (or expanding) the temporarily fixed film, the heating condition is usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, by irradiating ultraviolet rays from the substrate side, in the method for peeling to lower the adhesive strength of the temporary fixing film, dose of the ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

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

  The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred. As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

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

  When forming the via hole, if the material for forming the rewiring layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring layer (insulating layer) is irradiated with active energy rays through a mask pattern. The outermost wiring layer of the part is photocured.

  Examples of active energy rays 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 according to the photosensitive resin. As the exposure method, a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer (insulating layer) and exposure, and a mask pattern is exposed using parallel rays without being brought into close contact with the rewiring formation layer (insulating layer). Any non-contact exposure method may be used.

  Next, the rewiring formation layer (insulating layer) is developed, and the unexposed portion is removed to form a via hole. As the development, both wet development and dry development are suitable. A known developer can be used as the developer used in the 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 for forming the rewiring layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like. preferable. Laser irradiation can be performed using any suitable laser processing machine that uses a carbon dioxide laser, UV-YAG laser, excimer laser, or the like as a light source.

  The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

  The shape of the via hole, that is, the shape of the outline 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 (the diameter of the opening on the surface of the rewiring layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Although a minimum is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.

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

<Process (G)>
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 insulating properties at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. . As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

  Further, in the step (G), a bumping process for forming bumps may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. The via hole can be formed in the bumping process in the same manner as in the step (E).

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

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

  The third aspect of the semiconductor chip package of the present invention includes, for example, a rewiring formation layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. It is the semiconductor chip package manufactured with the resin composition or resin sheet of invention.

[Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles ( For example, various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like) can be given.

  EXAMPLES The present invention will be specifically described below 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) in Synthesis Example 1]
In a reaction vessel, difunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) 69 g and ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu) 40 g of petrochemicals) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added with further stirring, and the reaction was performed for about 3 hours. Next, after cooling the reaction product to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g / eq.) And 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. 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 at 2250 cm ⁻¹ was confirmed by FT-IR. The 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 the component (E) of Synthesis Example 1 having a butadiene structure and a phenolic hydroxyl group (phenolic) Hydroxyl-containing butadiene resin: non-volatile content: 50% by mass). The number average molecular weight was 5500.

[Synthesis Example 2: Synthesis of Component (E) in Synthesis Example 2]
A flask equipped with a stirrer, a thermometer and a condenser was charged with 292.09 g of ethyl diglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by ExxonMobil) as a solvent, and 100.1 g of 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. Subsequently, 195.9 g (0.2 mol) of nonylphenol novolac resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) and ethylene glycol bisanhydro trimellitate 41.0 g ( 0.1 mol), heated to 150 ° C. over 2 hours, and allowed to react for 12 hours, whereby the component (E) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group (phenolic hydroxyl group-containing butadiene) Resin: Non-volatile content 55.2% by mass).

[Example 1]
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), 10 parts, naphthalene 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 Corporation, epoxy equivalent: 90 to 105 g / eq), curing 1 part of an accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 300 parts of the component (E) synthesized in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), aliphatic Modified phenolic resin ("ELPC75" manufactured by Gunei Chemical Co., phenolic hydroxyl group equivalent: 215 g / eq, general formula ( ) And 6 parts of a resin containing a structural unit represented by the general formula (2), SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)), and spherical silica (Admatex) Manufactured, average particle diameter 1 μm) 950 parts were mixed and dispersed uniformly with a planetary mixer to prepare resin composition 1.

[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, synthesis 18 parts of component (E) synthesized in Example 2, 16 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g / eq), naphthalene type epoxy resin ("HP4032" manufactured by DIC, epoxy equivalent) About 144 g / eq) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq) 10 parts, curing accelerator (Shikoku Kasei “1B2PZ”, 1-benzyl- 1 part of 2-phenylimidazole), active ester type curing agent (manufactured by DIC "HPC-8000-6" T ”, an active group equivalent of about 225, a toluene solution of 65% by mass of a non-volatile component) 26.2 parts, an aliphatic modified phenolic resin (“ ELPC75 ”manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq), 15 parts, 700 parts of spherical silica (manufactured by Admatechs, average particle size 1 μm) surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) and 50 parts of cyclohexanone are mixed, and a planetary mixer To uniformly disperse the resin composition 2.

[Example 3]
In Example 1, the amount of the aliphatic modified phenolic resin (“ELPC75” manufactured by Gunei Chemical 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 phenolic resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) was changed from 6 parts to 4 parts. A resin composition 4 was produced in the same manner as in Example 1 except for the above items.

[Example 5]
In Example 1,
1) 20 parts of a naphthalene type epoxy resin (“NSN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330) is changed to 10 parts of a naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 330),
2) 950 parts of spherical silica (manufactured by Admatechs, average particle size 1 μm) surface-treated with SO-C4 (aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) was added 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 Co., Ltd.)
3) Furthermore, 300 parts of phenoxy resin (“YX7180BH40” manufactured by Mitsubishi Chemical Co., Ltd., solid content: 40%, MEK / cyclohexanone mixed solution) was added.
A resin composition 5 was produced 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 naphthalene type epoxy resin (“HP4032” manufactured by DIC, epoxy equivalent of about 144), liquid epoxy at 25 ° C. Resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 10 parts of a 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), aliphatic modified phenolic resin ( “ELPC75” manufactured by Gunei Chemical Co., Ltd., 20 parts of phenolic hydroxyl group equivalent: 215 g / eq), spherical silica (average particle size) treated with spherical silica A (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) diameter 1.3 .mu.m, specific surface area 7.1m ² / g) 155 parts of a curing accelerator (manufactured by Shikoku Chemicals Corporation, "1B2PZ", 1- benzyl The resin composition 6 was prepared 2-phenyl-imidazole) were uniformly dispersed in 1 part were mixed planetary mixer.

[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 of 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 Resin (“ELPC75” manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl group equivalent: 215 g / eq) 20 parts, SO—C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) surface-treated spherical silica ( 155 parts manufactured by Admatechs Co., Ltd., average particle diameter 1 μm, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd.), 1-ben Uniformly dispersed to prepare a resin composition 7 in-2-phenylimidazole) 1 part were mixed planetary mixer.

[Comparative Example 1]
In Example 1, 6 parts of an aliphatic modified phenolic resin ("ELPC75" manufactured by Gunei Chemical Co., Ltd., phenolic hydroxyl equivalent: 215 g / eq) was added to a cresol novolac resin ("KA-1160" manufactured by DIC), phenolic hydroxyl equivalent. : 117 g / 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 (“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) at 25 ° C., 20 parts, 20 parts of xylenol type epoxy resin (Mitsubishi Chemical "YX4000HK", epoxy equivalent of about 185), aliphatic modified phenolic resin ("ELPC75", Gunei Chemical Co., Ltd., phenolic hydroxyl equivalent: 215 g / eq), curing acceleration 1 part of an agent (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), 300 parts of the component (E) synthesized in Synthesis Example 2, SO-C4 (aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) 950 parts of spherical silica (manufactured by Admatechs, average particle diameter of 1 μm) surface-treated with “KBM573”) Uniformly dispersed in a planetary mixer to prepare a resin composition 9.

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

<Measurement of share strength>
On the silicon wafer to which the polyimide was applied, the resin compositions prepared in Examples and Comparative Examples were filled 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 shear strength at the interface between the polyimide and the test piece was measured with a bond tester (Dage series 4000) under the conditions that the head position was 1 mm from the base material and the head speed was 700 μm / s. The test was performed 5 times and the average value was used.

<Measurement of fracture bending strain>
The resin compositions prepared in Examples and Comparative Examples were compression molded on a release-treated SUS plate with a compression molding apparatus so as to have a thickness of 300 μm at 120 ° C. Thereafter, the resin composition was peeled off from the SUS plate and thermally cured at 180 ° C. for 90 minutes to obtain a test piece for measuring the breaking bending strain. Using a tensile tester “RTC-1250A” manufactured by Orientec, the breaking bending strain (%) at 23 ° C. was determined. The test was performed 5 times and the average value was used.

<Measurement of crackability>
The resin compositions prepared in Examples and Comparative Examples were compression molded on a release-treated SUS plate using a compression molding apparatus so as to have a thickness of 100 μm at 120 ° C. Thereafter, the resin composition was peeled off from the SUS plate and thermally cured under the condition 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]
(Double-circle): Even if it presses strongly, a crack does not arise.
○: Cracks do not occur even when pressed weakly.
Δ: Cracks occur when pressed hard.
X: Cracks occur when pressed weakly.

<Measurement of dielectric loss tangent and relative permittivity>
The resin compositions prepared in Examples and Comparative Examples were compression molded on a release-treated SUS plate with a compression molding apparatus so as to have a thickness of 200 μm at 120 ° C. Thereafter, the resin composition was peeled off from the SUS plate and thermally cured at 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 its relative dielectric constant and dielectric loss tangent at a measurement frequency of 5.8 GHz at a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP 8362B apparatus manufactured by Agilent Technologies.

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

  In each Example, even if it does not contain (D)-(G) component, although it is different in a grade, it has confirmed that it results in the same result as the said Example.

100 Semiconductor Chip Package 110 Semiconductor Chip 120 Sealing Layer 130 Rewiring Formation Layer (Insulating Layer)
140 Conductor layer (rewiring layer)
150 Solder resist layer 160 Bump

Claims (13)

(A) epoxy resin,
A resin composition comprising (B) an inorganic filler, and (C) a novolac-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.)   (B) The resin composition of Claim 1 whose content of a component is 30 to 95 mass% when the non-volatile component in a resin composition is 100 mass%.   The resin composition according to claim 1 or 2, wherein the content of the component (C) is 1% by mass to 15% by mass when 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) contains (A-1) a nitrogen-containing epoxy resin or an epoxy resin having a condensed ring structure.   The resin composition according to claim 4, wherein the component (A) further contains an epoxy resin that is liquid at 25 ° C. other than the components (A-2) and (A-1).   The quantity ratio ((A-1) component: (A-2) component) of the component (A-1) and the component (A-2) satisfies a relationship of 1: 0.1 to 1:10. 5. The resin composition according to 5.   Furthermore, (D) The resin composition of any one of Claims 1-6 containing a thermoplastic resin.   The resin composition according to any one of claims 1 to 7, which is a resin composition for an insulating layer of a semiconductor chip package.   The resin sheet which has a support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-7.   The resin sheet according to claim 9, which is a resin sheet for an insulating layer of a semiconductor chip package.   The circuit board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-8.   A semiconductor chip package comprising the circuit board according to claim 11 and a semiconductor chip mounted on the circuit board.   The semiconductor chip package containing the semiconductor chip sealed with the resin composition of any one of Claims 1-8, or the resin sheet of Claim 9.

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