JP2023095864A - resin composition - Google Patents

Abstract

To provide a resin composition which is excellent in insulation reliability, suppresses generation of warpage, and has a low coefficient of linear expansion, and a resin sheet using the same, a circuit board and a semiconductor chip package.SOLUTION: A resin composition for forming a resin sheet having a support, and a resin composition layer which is provided on the support and contains a resin composition contains (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler, wherein the component (a) has one or more structural units selected from a butadiene structural unit, a polysiloxane structural unit, a (meth)acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structure unit, and a polycarbonate structural unit, the component (a) is one or more selected from a resin having a glass transition temperature of 25°C or lower and a resin that is a liquid at 25°C, or the component (a) has a number average molecular weight (Mn) in terms of polystyrene measured using GPC (gel permeation chromatography) is 1,000-1,000,000, the component (b1) is a glycidylamine type epoxy resin, the component (b2) is a biphenyl type epoxy resin, when a non-volatile component of the resin composition is 100 mass%, the content of the component (C) is 50-95 mass%, a relative dielectric constant at 23°C and a measurement frequency of 5.8 GHz of a cured product obtained by thermosetting the resin composition at 180°C for 1 hour is 3.5 or less, and a difference between the relative dielectric constant and a relative dielectric constant at 23°C and a measurement frequency of 1 GHz of the cured product is 0.3 or less.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. Furthermore, it relates to a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.

In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and along with this, the insulating materials (insulating layers) for semiconductor packages used in these small electronic devices are also required to have higher functionality. It is

Such an insulating layer is known to be formed by curing a resin composition (see, for example, Patent Document 1).

JP 2015-82535 A

2. Description of the Related Art In recent years, there has been a demand for manufacturing smaller semiconductor packages, and thinner insulating layers are required for use in semiconductor packages. Therefore, excellent insulation reliability, suppression of warpage, and low coefficient of thermal expansion (CTE) are required.

However, insulation reliability, amount of warpage, and CTE are in a trade-off relationship, especially when the thickness of the insulation layer is thin. It was a problem that should be solved by

The present invention has been made to solve the above problems, and provides a resin composition that provides an insulating layer with excellent insulation reliability, suppressed warping, and a low coefficient of linear thermal expansion; An object of the present invention is to provide a sheet, a circuit board, and a semiconductor chip package.

The present inventors have incorporated (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and a predetermined amount of (c) an inorganic filler, Furthermore, the cured product obtained by heat curing at 180 ° C. for 1 hour has an elastic modulus at 23 ° C. of 18 GPa or less, a relative dielectric constant at a measurement frequency of 5.8 GHz at 23 ° C. of 3.5 or less, and 23 By satisfying the requirement that the difference between the dielectric constant at a measurement frequency of 1 GHz and the dielectric constant at °C is 0.3 or less, it is possible to obtain an insulating layer with excellent insulation reliability, suppressed warping, and a low coefficient of linear thermal expansion. and completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler,
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass,
The elastic modulus at 23° C. of a cured product obtained by thermally curing the resin composition at 180° C. for 1 hour is 18 GPa or less,
The cured product has a relative dielectric constant of 3.5 or less at a measurement frequency of 5.8 GHz at 23 ° C., and a difference from the relative dielectric constant of the cured product at a measurement frequency of 1 GHz at 23 ° C. is 0.3 or less. Resin composition.
[2] A cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour has a dielectric loss tangent of 0.01 or less at a measurement frequency of 5.8 GHz at 23 ° C., and a measurement frequency of 1 GHz at 23 ° C. The resin composition according to [1], wherein the difference from the dielectric loss tangent is 0.002 or less.
[3] The content of component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding component (c) is taken as 100% by mass, [1] or [2] The resin composition according to .
[4] Component (a) is selected from butadiene structural units, polysiloxane structural units, (meth)acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. The resin composition according to any one of [1] to [3], which has one or more structural units.
[5] The component (a) according to any one of [1] to [4], wherein the component (a) is one or more selected from resins having a glass transition temperature of 25°C or less and resins that are liquid at 25°C. Resin composition.
[6] The resin composition according to any one of [1] to [5], wherein component (a) has a functional group capable of reacting with components (b1) and (b2).
[7] The resin composition according to any one of [1] to [6], wherein component (a) has a phenolic hydroxyl group.
[8] The composition according to any one of [1] to [7], further comprising (d) a curing agent, and the curing agent is one or more selected from phenol-based curing agents and active ester curing agents. Resin composition.
[9] The resin composition according to any one of [1] to [8], which is a resin composition for insulating layers of semiconductor chip packages.
[10] A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [9] provided on the support.
[11] The resin sheet according to [10], which is a resin sheet for an insulating layer of a semiconductor chip package.
[12] A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to [12].
[14] A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of [1] to [9] or the resin sheet according to [10].

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a resin composition that provides an insulating layer with excellent insulation reliability, suppressed warping, and a low coefficient of linear thermal expansion; a resin sheet, a circuit board, and a semiconductor chip package using the same. can do.

FIG. 1 is a schematic cross-sectional view showing an example of a method of manufacturing a circuit board according to the present invention, in which step (3) is a step of forming via holes in insulating layers, forming conductor layers, and connecting wiring layers between layers. It is a diagram. FIG. 2 is a schematic cross-sectional view showing an example in which the step (3) is a step of polishing or grinding an insulating layer, exposing a wiring layer, and connecting the wiring layers between layers in the method of manufacturing a circuit board of the present invention. It is a diagram. FIG. 3 is a schematic cross-sectional view showing an example of the semiconductor chip package (fan-out type WLP) of the present invention.

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

[Resin composition]
The resin composition of the present invention comprises (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler. The content of component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass, and the resin composition is heat cured at 180 ° C. for 1 hour. The cured product has an elastic modulus of 18 GPa or less at 23 ° C., a dielectric constant of 3.5 or less at a measurement frequency of 5.8 GHz at 23 ° C., and a measurement frequency of 1 GHz at 23 ° C. is 0.3 or less.

(a) component, (b1) component, (b2) component, and a predetermined amount of (c) component are contained in the resin composition, and the elastic modulus and dielectric constant of the cured product are within a predetermined range. Therefore, it is possible to obtain an insulating layer that has excellent insulation reliability, suppresses the occurrence of warpage, and has a low coefficient of linear thermal expansion. The resin composition may further contain (d) a curing agent, (e) a curing accelerator, and (f) a flame retardant, if necessary. Each component contained in the resin composition will be described in detail below.

<(a) Elastomer>
The resin composition contains (a) an elastomer. In the present invention, the elastomer means a resin having flexibility, and is not particularly limited. , an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit, thereby exhibiting flexibility. By including a flexible resin such as the component (a), it is possible to obtain an insulating layer that is excellent in insulation reliability, suppresses the occurrence of warpage, and has a low coefficient of linear thermal expansion. In addition, "(meth)acrylate" refers to methacrylate and acrylate.

More specifically, component (a) includes butadiene structural units such as polybutadiene and hydrogenated polybutadiene, polysiloxane structural units such as silicone rubber, (meth)acrylate structural units, alkylene structural units (preferably having 2 to 15, more preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), an alkyleneoxy structural unit ((preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably has 5 to 6 carbon atoms), an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. It preferably has one or more structural units selected from meth)acrylate structural units, isoprene structural units, isobutylene structural units, or polycarbonate structural units, and is selected from butadiene structural units and (meth)acrylate structural units. It is more preferable to have one or more structural units that are

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

Component (a) is preferably one or more resins selected from resins having a glass transition temperature (Tg) of 25°C or less and resins that are liquid at 25°C, in order to exhibit flexibility.

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

Component (a) is not particularly limited as long as it is a flexible resin. It is preferable to have a functional group capable of reacting with. The functional group capable of reacting with the component (b) includes a functional group that appears upon heating.

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

A preferred embodiment of component (a) is butadiene resin. As the butadiene resin, a butadiene resin that is liquid at 25°C or has a glass transition temperature of 25°C or less is preferable. hydroxyl group-containing butadiene resin), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin. more preferred. Here, "butadiene resin" refers to a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or in the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a portion of the polybutadiene skeleton is hydrogenated, and does not necessarily have to be a resin in which the polybutadiene skeleton is completely hydrogenated.

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

When the butadiene resin has a functional group, the functional group equivalent is preferably 100-10,000, more preferably 200-5,000. Note that the functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of butadiene resins include Clay Valley's "Ricon 657" (epoxy group-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", " Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (acid anhydride group-containing polybutadiene), Nippon Soda Co., Ltd. "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" ( Hydroxy group- and carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both hydroxyl-terminated polybutadiene), "GI-1000", "GI-2000", "GI-3000" ( Hydrogenated polybutadiene with both hydroxyl groups), Daicel's "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene and styrene block epoxidized copolymer), Nagase ChemteX Co., Ltd. "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin), and the like.

In addition, as another preferred embodiment of the component (a), a linear polyimide made from a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083, International Publication No. 2008/153208 Polyimide described in No.) can also be used. The butadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to in JP-A-2006-37083 and WO 2008/153208, the contents of which are incorporated herein.

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

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

When the acrylic resin has a functional group, the functional group equivalent is preferably 1,000 to 50,000, more preferably 2,500 to 30,000.

Specific examples of acrylic resins include Teisan Resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (carboxy group Containing acrylic acid ester copolymer resin, acid value 5-34 mgKOH/g, weight average molecular weight 400,000-900,000, Tg-30-5°C), "SG-80H", "SG-80H-3", "SG -P3" (epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761-14285 g/eq, weight average molecular weight 350,000-850,000, Tg 11-12°C), "SG-600TEA", "SG-790" ( Hydroxy group-containing acrylate copolymer resin, hydroxyl value 20 to 40 mgKOH/g, weight average molecular weight 500,000 to 1,200,000, Tg -37 to -32°C), "ME-2000" manufactured by Negami Kogyo Co., Ltd., "W -116.3" (carboxy group-containing acrylic ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic ester copolymer resin), "KG-25", "KG-3000" (epoxy group-containing acrylic acid ester copolymer resin) and the like.

A preferred embodiment of component (a) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25° C. or less is preferable, and a hydroxyl group-containing carbonate resin (more preferably a phenolic hydroxyl group-containing carbonate resin), a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, or a One or more resins selected from the group consisting of containing carbonate resins, isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred. Here, "carbonate resin" means a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or in the side chain.

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

Specific examples of carbonate resins include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. etc.

A linear polyimide (PCT/JP2016/053609) made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The carbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be referred to the description of PCT/JP2016/053609, the content of which is incorporated herein.

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

Specific examples of polysiloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimides made from tetrabasic acid anhydride ( International Publication No. 2010/053185) and the like. Specific examples of alkylene resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers. Specific examples of isoprene resins include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation.

Furthermore, preferred embodiments of component (a) include acrylic rubber particles, polyamide fine particles, silicone particles, and the like. Specific examples of acrylic rubber particles include fine particles of resins made insoluble and infusible in organic solvents by chemically cross-linking resins exhibiting rubber elasticity, such as acrylonitrile-butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) ) and the like. Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, and polyamideimides, as long as they have flexible skeletons. ) and SP500 (manufactured by Toray Industries, Inc.).

From the viewpoint of imparting flexibility, the content of component (a) in the resin composition is preferably 85% by mass or less, more preferably 85% by mass or less, when the non-volatile component of the resin composition excluding component (c) is taken as 100% by mass. is 80% by mass or less, more preferably 75% by mass or less, and even more preferably 73% by mass or less. Also, the lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 45% by mass or more, and even more preferably 55% by mass or more.

<(b1) Liquid Epoxy Resin Having Aromatic Structure, and (b2) Solid Epoxy Resin Having Aromatic Structure>
The resin composition contains (b1) a liquid epoxy resin having an aromatic structure and (b2) a solid epoxy resin having an aromatic structure. (b1) A liquid epoxy resin having an aromatic structure (hereinafter sometimes simply referred to as a "liquid epoxy resin") refers to an epoxy resin having an aromatic structure that is liquid at a temperature of 20°C. preferably has two or more epoxy groups. The (b2) solid epoxy resin having an aromatic structure (hereinafter sometimes simply referred to as "solid epoxy resin") is an epoxy resin having an aromatic structure that is solid at a temperature of 20°C. No, it is preferable to have 3 or more epoxy groups in one molecule. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. In the present invention, by using a liquid epoxy resin and a solid epoxy resin in combination, the compatibility of the component (a) is improved, and a resin composition having excellent flexibility can be obtained.

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin having an aromatic structure, and glycidylamine-type epoxy resin having an aromatic structure. , phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton having an aromatic structure, cyclohexane dimethanol type epoxy resins having an aromatic structure, and epoxy resins having a butadiene structure having an aromatic structure are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation, and "828US" and "jER828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation. , "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (aminophenol type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ” (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” manufactured by Daicel Corporation (having an ester skeleton alicyclic epoxy resin), and "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane). These may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the liquid epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving the compatibility of the component (a) when the non-volatile component in the resin composition is 100% by mass. is 2% by mass or more, more preferably 2.5% by mass or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

The epoxy equivalent of the liquid epoxy resin is preferably 50-5000, more preferably 50-3000, still more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition is sufficient, and when the cured product is used as an insulating layer, an insulating layer with a small surface roughness can be obtained. The epoxy equivalent of the liquid epoxy resin can be measured according to JIS K7236, and is the mass of the resin containing one equivalent of epoxy groups.

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

Solid epoxy resins include naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin having an aromatic structure, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, and naphthylene. Ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, tetraphenylethane-type epoxy resin are preferred, naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthyl A lene ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" ( cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" ( dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN" manufactured by Nippon Kayaku Co., Ltd. -502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol-type epoxy resin), "ESN485" (naphthol-novolac-type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin) , "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene 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) manufactured by Mitsubishi Chemical Corporation "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals, "YL7800" (fluorene type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of adjusting the viscosity of the resin composition, the content of the solid epoxy resin in the resin composition is preferably 0.1% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.2% by mass or more, more preferably 0.3% by mass or more. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

The epoxy equivalent weight of the solid epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent of a solid epoxy resin can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

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

When the content of the liquid epoxy resin is B1 (% by mass) and the content of the solid epoxy resin is B2 (% by mass), it is preferable to satisfy the relationship B1>B2 from the viewpoint of adjusting the melt viscosity. Further, the difference between B1 and B2 (B1-B2) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, 0.5% by mass or more, Or it is 1% by mass or more. Although the upper limit of the difference (B1-B2) is not particularly limited, it can usually be 10% by mass or less, 5% by mass or less, or the like.

The mass ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin/liquid epoxy resin) is preferably in the range of 0.01 to 1. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) when used in the form of a resin sheet, moderate adhesiveness is provided, and ii) when used in the form of a resin sheet. iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin/liquid epoxy resin) is preferably in the range of 0.05 to 0.8. Preferably, the range of 0.1 to 0.5 is more preferable.

<(c) Inorganic filler>
The resin composition contains (c) an inorganic filler. The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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. Among these, silica is particularly suitable. 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 diameter of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with low surface roughness. It is preferably 2 μm or less. Although the lower limit of the average particle size is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include “YC100C”, “YA050C”, “YA050C-MJE” and “YA010C” manufactured by Admatechs, and “UFP-30” manufactured by Denki Kagaku Kogyo. ”, Tokuyama “Sylfil NSS-3N”, “Silfil NSS-4N”, “Sylfil NSS-5N”, Admatechs “SC2500SQ”, “SO-C6”, “SO-C4”, “SO-C2 ”, “SO-C1” and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd. can be used.

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanates, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated 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 Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), and the like.

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

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content of the inorganic filler in the resin composition is 50% by mass to 95% by mass from the viewpoint of obtaining an insulating layer with a low dielectric constant and a low coefficient of thermal expansion. It is preferably 55% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of mechanical strength, particularly elongation, of the insulating layer.

<(d) Curing agent>
The resin composition may contain (d) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as component (b). Examples include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate esters curing agents, carbodiimide curing agents, and the like. A single curing agent may be used alone, or two or more curing agents may be used in combination. Component (d) is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents. It is preferably one or more selected from agents.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

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

An active ester curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer. The active ester-based curing agent is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more 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 preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H- 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 phenol novolac ( Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be mentioned as active ester curing agents that are benzoylated phenol novolacs.

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

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

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

When the resin composition contains component (d), the content of the curing agent in the resin composition is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass. It is below. Moreover, the lower limit is not particularly limited, but 1% by mass or more is preferable.

<(e) Curing accelerator>
The resin composition may contain (e) a curing accelerator. Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metallic curing accelerators are preferred, and amine-based curing accelerators, imidazole-based curing accelerators, and metallic curing accelerators are more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. and the like, organic iron 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 organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains component (e), the content of the curing accelerator in the resin composition is not particularly limited. 0.01% by mass to 3% by mass is preferable.

<(f) flame retardant>
The resin composition may contain (f) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As the flame retardant, a commercially available product may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd. and the like.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably 0.5% by mass to 10% by mass is more preferable.

<(g) optional additive>
The resin composition may further contain other additives as necessary, such other additives as, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, Also included are resin additives such as binders, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and colorants.

<Physical properties of the resin composition>
A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 1 hour has an elastic modulus at 23° C. of 18 GPa or less, preferably 15 GPa or less, 13 GPa or less, 11 GPa or less, or 10 GPa or less. is more preferable. Although the lower limit is not particularly limited, it can be, for example, 0.01 GPa or more, 0.5 GPa or more, or 1 GPa or more. By setting the elastic modulus to 18 GPa or less, it is possible to suppress the occurrence of warping of the cured product. The elastic modulus can be measured according to the method described in <Measurement of Elastic Modulus> below.

A cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour has a relative dielectric constant at a measurement frequency of 5.8 GHz at 23 ° C. of 3.5 or less, preferably 3.4 or less. It is more preferably 3.3 or less. Although the lower limit is not particularly limited, it can be, for example, 1 or more, 1.1 or more, or 1.2 or more. By setting the thickness within the above range, the CTE can be lowered and the amount of warpage can be suppressed. The dielectric constant can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour preferably has a dielectric constant of 3.6 or less at a measurement frequency of 1 GHz at 23 ° C., more preferably 3.5 or less. It is preferably 3.4 or less, more preferably 3.4 or less. Although the lower limit is not particularly limited, it can be, for example, 1 or more, 1.1 or more, or 1.2 or more. By setting the thickness within the above range, the CTE can be lowered and the amount of warpage can be suppressed. The dielectric constant can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

In addition, the relative dielectric constant at a measurement frequency of 5.8 GHz at 23 ° C. of the cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour, and the relative dielectric constant at a measurement frequency of 1 GHz at 23 ° C. of the cured product. The difference is 0.3 or less, preferably 0.25 or less, more preferably 0.23 or less, further preferably 0.2 or less, 0.15 or less, 0.1 Below, it is more preferably 0.05 or less, 0.005 or less, or 0.002 or less. The lower limit is not particularly limited, but can be, for example, 0 or more, 0.001 or more. By setting the thickness within the above range, it is possible to obtain an insulating layer that has excellent insulation reliability, suppresses warpage, and has a low CTE. The difference in dielectric constant can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour preferably has a dielectric loss tangent at a measurement frequency of 5.8 GHz at 23 ° C. of 0.01 or less, preferably 0.009 or less. It is more preferably 0.008 or less. The lower limit is not particularly limited, but may be, for example, 0, 0.0001 or more. By setting the thickness within the above range, it is possible to provide an insulating layer capable of suppressing the insertion loss to a low level. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 1 hour preferably has a dielectric loss tangent at a measurement frequency of 1 GHz at 23° C. of 0.01 or less, more preferably 0.009 or less. , 0.008 or less. The lower limit is not particularly limited, but may be, for example, 0, 0.0001 or more. By setting the thickness within the above range, it is possible to provide an insulating layer capable of suppressing the insertion loss to a low level. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

The difference between the dielectric loss tangent at a measurement frequency of 5.8 GHz at 23 ° C. of the cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour and the dielectric loss tangent at a measurement frequency of 1 GHz at 23 ° C. is 0. It is preferably 0.002 or less, more preferably 0.001 or less, and even more preferably 0.0005 or less. Although the lower limit is not particularly limited, it may be 0 or more, for example. By setting the thickness within the above range, it is possible to provide an insulating layer capable of keeping the insertion loss low. The difference in dielectric loss tangent can be measured according to the method described in <Measurement of dielectric constant and dielectric loss tangent> described later.

A cured product obtained by thermally curing the resin composition of the present invention at 100° C. for 30 minutes and further at 180° C. for 30 minutes exhibits the property of suppressing warping. The amount of warp is preferably less than 2 cm, more preferably 1.5 cm or less, more preferably 1 cm or less. The warp can be measured according to the method described in <Evaluation of Warp Amount> below.

A cured product obtained by thermally curing the resin composition of the present invention at 180° C. for 1 hour has an insulation resistance value (insulation reliability in humidity characteristics) give good results. The resistance value is preferably 10 ⁸ Ω or more, more preferably 10 ⁹ Ω or more, and still more preferably 10 ¹⁰ Ω or more. The wet insulation reliability can be measured according to the method described later in <Evaluation of wet insulation reliability>.

The linear thermal expansion coefficient (CTE) of the cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour is preferably 20 ppm / ° C. or less, more preferably 15 ppm / ° C. or less, from the viewpoint of suppressing warpage. More preferably, it is 10 ppm/°C or less. Although the lower limit is not particularly limited, it may be 1 ppm/° C. or more. The coefficient of linear thermal expansion can be measured according to the procedure of <measurement of coefficient of linear thermal expansion (CTE)> described later.

The resin composition of the present invention has excellent insulation reliability, suppresses the occurrence of warping, and can provide an insulating layer with a low coefficient of linear thermal expansion. a) The compatibility of the components is good. Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). It can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board) for forming an interlayer insulating layer on which a conductor layer is formed by plating (plating It can be further preferably used as an interlayer insulating layer resin composition) of a circuit board forming a conductor layer by.
It is also suitable as a resin composition for sealing a semiconductor chip (semiconductor chip sealing resin composition) and a resin composition for forming wiring on a semiconductor chip (semiconductor chip wiring forming resin composition). can be used.

[Resin sheet]
The resin sheet of the present invention comprises a support and a resin composition layer bonded to the support, and the resin composition layer comprises 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, even more 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 lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 5 μm or more, or 10 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

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

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. 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 carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes The resin composition layer can be formed.

In the resin sheet, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as base materials for prepreg, such as glass cloth, aramid nonwoven fabric, and 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, even more preferably 700 μm or less, and even more preferably 600 μm or less. Although the lower limit of the thickness of the sheet-like fiber base material is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

A prepreg can be manufactured 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.

The resin sheet of the present invention can be suitably used for forming an insulating layer in the manufacture of semiconductor chip packages (insulating resin sheet for semiconductor chip packages).
For example, the resin sheet of the present invention can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and can be used for interlayer insulation in which a conductor layer is formed thereon by plating. It can be more suitably used for forming layers (for interlayer insulating layers of circuit boards on which conductive layers are formed by plating). Examples of packages using such substrates include FC-CSP, MIS-BGA packages, and ETS-BGA packages.
Further, the resin sheet of the present invention can be suitably used for encapsulating a semiconductor chip (semiconductor chip encapsulating resin sheet) or for forming wiring on a semiconductor chip (semiconductor chip wiring forming resin sheet). For example, it can be suitably used for fan-out type WLP (wafer level package), fan-in type WLP, fan-out type PLP (panel level package), fan-in type PLP and the like. It can also be suitably used as a MUF (Molding Under Filling) material used after connecting a semiconductor chip to a substrate.
The resin sheet of the present invention can also be suitably used for a wide range of other applications requiring high insulation reliability, for example, for forming insulating layers of circuit boards such as printed wiring boards.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.
As shown in FIGS. 1 and 2, the circuit board manufacturing method of the present invention includes:
(1) 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;
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, followed by thermal curing to form an insulating layer;
(3) A step of connecting wiring layers between layers is included. Moreover, the method for manufacturing a circuit board may include (4) a step of removing the base material.

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

<Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer, which has a substrate and a wiring layer provided on at least one surface of the substrate. As shown in an example in FIGS. 1A and 2A, the substrate 10 with a wiring layer includes a first metal layer 12 and a second metal layer which are part of the substrate 11 on both sides of the substrate 11. 13 respectively, and a wiring layer 14 is provided on the surface of the second metal layer 13 opposite to the surface facing the substrate 11 . Specifically, a dry film (photosensitive resist film) is laminated on a base material, exposed under predetermined conditions using a photomask, and developed to form a patterned dry film. After forming a wiring layer by electroplating using the developed patterned dry film as a plating mask, the patterned dry film is peeled off. 1 and 2 show the embodiment having the first metal layer 12 and the second metal layer 13, the first metal layer 12 and the second metal layer 13 may be omitted.

Examples of the base material include substrates such as glass epoxy substrates, metal substrates (stainless steel, cold-rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. A metal layer such as copper foil may be formed on the surface. Also, as shown in FIGS. 1A and 2A, a first metal layer 12 and a second metal layer 13 that can be peeled off on the surface (for example, an ultra-thin copper foil with a carrier copper foil manufactured by Mitsui Kinzoku Co., Ltd.) , trade name “Micro Thin”) or the like may be formed.

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

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

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

The line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, further preferably 5/ It is 5 µm or less, more preferably 1/1 µm or less, and particularly preferably 0.5/0.5 µm or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layers 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 plating using a dry film having a desired pattern formed thereon as a plating mask.

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

The 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 μm, depending on the desired wiring board design. When the step (3) employs a step of polishing or grinding the insulating layer to expose the wiring layer and connect the wiring layers between layers, it is preferable that the thickness of the wiring to be connected between layers and the thickness of the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers is preferably 100 μm or less and 2 μm or more depending on the design of the desired wiring board. Moreover, the wiring for interlayer connection may be convex.

After forming the wiring layer, the dry film is peeled off. Stripping of the dry film can be carried out using, for example, an alkaline stripping solution such as sodium hydroxide solution. If necessary, a desired wiring pattern can be formed by removing unnecessary wiring patterns by etching or the like. The pitch of the wiring layers 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 base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, followed by thermal curing to form an insulating layer. As an example is shown in FIG. 1B, the wiring layer 14 of the base material with the wiring layer obtained in the above step (1) is laminated so as to be embedded in the resin composition layer 21 of the resin sheet 20, The resin composition layer 21 of the resin sheet 20 is thermally cured to form an insulating layer (reference numeral 21' in FIG. 1(C) or FIG. 2(B)). The resin sheet 20 is formed by laminating a resin composition layer 21 and a support 22 in this order.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heating and press-bonding the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. Examples of the member for thermocompression bonding of the resin sheet to the wiring layer (hereinafter also referred to as "thermocompression member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the wiring layer.

Lamination of the wiring layer and the resin sheet may be carried out by a vacuum lamination method after removing the protective film of the resin sheet. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Lamination and smoothing may be performed continuously using the above-mentioned 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, the thermosetting conditions for the resin composition layer may vary depending on the type of resin composition, but the curing temperature may be in the range of 120° C. to 240° C., and the curing time may be in the range of 5 minutes to 120 minutes. Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature.

The support of the resin sheet may be separated after laminating the resin sheet on the substrate with the wiring layer and thermally curing it. As an example is shown in FIG. The support may be peeled off prior to lamination. Moreover, the support may be peeled off before the roughening treatment step described later.

<Step (3)>
Step (3) is a step of connecting wiring layers between layers. In detail, it is a step of forming via holes in an insulating layer, forming a conductor layer, and connecting wiring layers between layers (see FIGS. 1(C) and 1(D)). Alternatively, the insulating layer is polished or ground, the wiring layer is exposed, and the wiring layer is connected between layers (see FIG. 2C).

In the case of adopting a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting a wiring layer between layers, the formation of the via hole is not particularly limited. preferably performed 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, as shown in an example in FIG. 1C, in step (3), laser irradiation is performed from the surface side of the support 22 to penetrate the support 22 and the insulating layer 21' to form the wiring layer 14. An exposed via hole 31 is formed.

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

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

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

Before forming the conductor layer, the via hole and the insulating layer may be roughened. Roughening treatment can employ known procedures and conditions that are usually performed. An example of dry roughening treatment is plasma treatment, and an example of wet roughening treatment is a method in which swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution are performed in this order. is mentioned.

After forming the via holes, a conductor layer 40 is formed as shown in FIG. 1(D). The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable conventionally known method such as plating, sputtering, vapor deposition, etc., and is preferably formed by plating. In a preferred embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Further, when the support in the resin sheet is a metal foil, a conductive layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated.

Specifically, a plating seed layer 41 is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. An electrolytic plated layer 42 is formed on the exposed plating seed layer by electrolytic plating. At this time, along with the formation of the electroplating layer 42 , the via hole 31 may be filled by electroplating to form the filled via 61 . After forming the electrolytic plating layer 42, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and the conductor layer 40 having the desired wiring pattern can be formed. The dry film used for forming the mask pattern when forming the conductor layer is the same as the dry film described above.

The conductor layer can include not only linear wiring but also electrode pads (lands) on which external terminals can be mounted, for example. Alternatively, the conductor layer may be composed only of the electrode pads.

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

When a step of polishing or grinding an insulating layer and exposing the wiring layer to connect the wiring layer between layers is employed, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed, and the polished or ground surface can be exposed. is not particularly limited as long as it is horizontal, and conventionally known polishing methods or grinding methods can be applied. etc. A smear removal step and a roughening treatment step may be performed in the same manner as the step of forming via holes in an insulating layer, forming a conductor layer, and connecting wiring layers between layers, or a conductor layer may be formed. Moreover, as an example is shown in FIG. 2C, it is not necessary to expose the entire wiring layer 14, and a part of the wiring layer 14 may be exposed.

<Step (4)>
The circuit board manufacturing method may include a step (4) in addition to the steps (1) to (3). Step (4) is a step of removing the base material to form the circuit board 1 of the present invention, as shown in FIGS. 1(E) and 2(D). A method for removing the substrate is not particularly limited. In one preferred embodiment, the substrate is stripped from the circuit board at the interface of the first and second metal layers, and the second metal layer is etched away, such as with an aqueous copper chloride solution. If necessary, the substrate may be peeled off while the conductor layer is protected with a protective film.

[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 of the present invention. A semiconductor chip package can be manufactured by bonding a semiconductor chip to the circuit board of the present invention.

As long as the terminal electrodes of the semiconductor chip are conductively connected to the circuit wiring of the circuit board, the bonding conditions are not particularly limited, and known conditions used in flip-chip mounting of semiconductor chips may be used. Alternatively, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

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

Another preferred embodiment reflows and joins the semiconductor chip to the circuit board. The reflow conditions can be, for example, in the range of 120.degree. C. to 300.degree.

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

A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (fan-out type WLP) 100 as shown in FIG. It is a semiconductor chip package manufactured from a sheet. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed to cover the periphery of the semiconductor chip 110, and rewiring formed on the surface of the semiconductor chip 110 opposite to the side covered with the sealing layer. It includes a layer (insulating layer) 130 , a conductor layer (rewiring layer) 140 , a solder resist layer 150 and bumps 160 . A method for manufacturing such a semiconductor chip package includes:
(A) a step of laminating a temporary fixing film on a substrate;
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention onto a semiconductor chip and heat-curing to form a sealing layer;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring layer (insulating layer) on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed;
(F) forming a conductor layer (rewiring layer) on the rewiring layer (insulating layer); and (G) forming a solder resist layer on the conductor layer. Also, the method of manufacturing a semiconductor chip package may include the step of (H) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into individual pieces.

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

The material used for the base material is not particularly limited. Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); 4 substrate); and a substrate made of bismaleimide triazine resin (BT resin).

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

<Step (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporarily fixing the semiconductor chip can be performed using a known device such as a flip chip bonder and a die bonder. The layout and the number of arrangement of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, etc. For example, a matrix of multiple rows and multiple columns can be aligned and temporarily fixed.

<Step (C)>
The step (C) is a step of laminating the resin composition layer of the resin sheet of the invention on a semiconductor chip, or applying the resin composition of the invention onto a semiconductor chip and thermally curing it to form a sealing layer. be. In step (C), the resin composition layer of the resin sheet of the present invention is preferably laminated on a semiconductor chip and thermally cured to form a sealing layer.

The lamination of the semiconductor chip and the resin sheet can be carried out, for example, by heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter also referred to as "thermocompression member") include a heated metal plate (such as a SUS panel) or a metal roll (SUS roll). Instead of directly pressing the thermocompression member against the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the unevenness of the surface of the semiconductor chip.

Moreover, lamination of the semiconductor chip and the resin sheet may be carried out by a vacuum lamination method after removing the protective film of the resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) of the circuit board production method, and the preferred ranges are also the same.

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

<Step (D)>
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. The peeling method can be changed as appropriate depending on the material of the temporary fixing film, for example, a method of heating and foaming (or expanding) the temporary fixing film to peel it off, and a method of irradiating ultraviolet rays from the substrate side, A method of reducing the adhesive strength of the temporary fixing film and peeling it off is included.

In the method of heating and foaming (or expanding) the temporary fixing film to separate it, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of removing the adhesive force of the temporary fixing film by irradiating it with ultraviolet rays from the base material side, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

<Step (E)>
Step (E) is a step of forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed.

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

After forming the rewiring layer (insulating layer), a via hole may be formed in the rewiring layer (insulating layer) for interlayer connection between the semiconductor chip and a conductor layer to be described later.

In forming the via hole, if the material forming the rewiring layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring layer (insulating layer) is irradiated with an active energy ray through a mask pattern. The uppermost wiring layer of the part is photo-cured.

Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin. As for the exposure method, there is a contact exposure method in which the mask pattern is brought into close contact with the rewiring formation layer (insulating layer) for exposure, and an exposure using parallel light without making the mask pattern in 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 to remove the unexposed portions to form via holes. Both wet development and dry development are suitable for development. A known developer can be used as the developer used in the wet development.

The development method includes, for example, a dipping 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, but laser irradiation, etching, mechanical drilling, etc., can be mentioned. preferable. Laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas 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 carried out by any suitable process according to a conventional method according to the means selected.

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 the lower limit is not particularly limited, it is preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more.

<Step (F)>
Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulating layer) is the same as the method of forming the conductor layer after forming via holes in the insulating layer in step (3) in the method for manufacturing a circuit board, and is preferable. The same applies to the range. The steps (E) and (F) may be repeated to alternately build up the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers) (build-up).

<Step (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 when the solder resist layer is formed. From the viewpoint of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. . As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

Moreover, in the step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a known method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

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

In a third aspect of the semiconductor chip package of the present invention, 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. A semiconductor chip package manufactured from the resin composition or resin sheet of the invention.

[Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles ( Examples include various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" mean "mass parts" and "mass%", respectively, unless otherwise specified.

(Preparation of cured product for evaluation)
A release agent-treated PET film ("501010" manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square) was coated with a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works) on the untreated side of the release agent. , thickness 0.7 mm, 255 mm square) were overlapped and fixed on four sides with a polyimide adhesive tape (width 10 mm) (hereinafter, "fixed PET film").
PET film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C. , hereinafter “release PET”), the resin composition layer after drying is coated with a die coater so that the thickness is 40 μm, and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes. got a sheet. Each resin sheet (thickness 40 μm, 200 mm square) is treated with a release agent for a fixed PET film using a batch-type vacuum pressure laminator (2-stage build-up laminator, CVP700 manufactured by Nikko Materials Co., Ltd.). A resin sheet was obtained by laminating in the center so as to be in contact with the surface. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds.

Next, under the temperature condition of 100°C, the film was placed in an oven at 100°C for 30 minutes, and then under the temperature condition of 175°C, it was transferred to an oven at 175°C and then heat-cured for 30 minutes. After that, the substrate was taken out in an atmosphere of room temperature, the release PET was peeled off from the resin sheet with the support, and the substrate was placed in an oven at 190° C. and thermally cured under curing conditions for 90 minutes.

After thermal curing, the polyimide adhesive tape was peeled off, the cured product was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate, and the PET film ("501010" manufactured by Lintec Co., Ltd.) was also peeled off to obtain a sheet-like cured product. rice field. The resulting cured product is referred to as "evaluation cured product".

<Measurement of coefficient of linear thermal expansion (CTE)>
The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was performed twice continuously under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Then, in the two measurements, the linear thermal expansion coefficient (ppm/°C) in the planar direction was calculated in the range from 25°C to 150°C.

<Measurement of elastic modulus>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 specimen to obtain a test piece. The tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elastic modulus at 23°C was obtained. The measurement was carried out according to JIS K7127.

<Measurement of dielectric constant and dielectric loss tangent>
The resin varnishes obtained in Examples and Comparative Examples were applied onto a release-treated PET film (manufactured by Lintec, "PET501010"), and a die coater was applied so that the thickness of the resin composition layer after drying was 40 μm. and dried at 80 to 110°C (average 95°C) for 6 minutes. After that, the film was heat-treated at 180° C. for 1 hour and peeled from the support to obtain a cured film. The cured film was cut into a piece having a length of 80 mm and a width of 2 mm to obtain an evaluation sample. For this evaluation sample, the dielectric constant and the dielectric loss tangent were measured at a measurement temperature of 23° C. at a measurement frequency of 1 GHz or 5.8 GHz by a cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies. Two test pieces were measured, and the average value was calculated. Also, the difference between the relative permittivity (average value) at the measurement frequency of 1 GHz and the relative permittivity (average value) at the measurement frequency of 5.8 GHz was obtained, and the dielectric loss tangent (average value) at the measurement frequency of 1 GHz and the measurement frequency of 5.5 GHz were obtained. A difference from the dielectric loss tangent (average value) at 8 GHz was obtained.

<Evaluation of insulation reliability in humidity>
(Preparation of substrate for evaluation)
(1) Surface treatment of inner layer circuit board As the inner layer circuit board, glass cloth base epoxy resin double-sided copper having circuit conductors (copper) formed on both sides with a wiring pattern of 1 mm square grid (70% residual copper rate) A clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R1515F” manufactured by Panasonic Corporation) was prepared. Both surfaces of the inner layer circuit board were immersed in "CZ8100" manufactured by MEC Co., Ltd. to roughen the copper surface (copper etching amount: 0.7 μm).

(2) Lamination of resin sheets PET film ("Lumirror R80" manufactured by Toray Industries, Inc.) obtained by releasing each resin varnish prepared in Examples and Comparative Examples with an alkyd resin release agent ("AL-5" manufactured by Lintec) , thickness 38 μm, softening point 130° C., hereinafter referred to as “release PET”), coated with a die coater so that the thickness of the resin composition layer after drying is 35 μm, 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin sheet. The prepared resin sheet is placed on both sides of the inner layer circuit board using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator, CVP700) so that the resin composition layer is in contact with the inner layer circuit board. laminated to. Lamination was carried out by pressure bonding for 30 seconds at a pressure of 120° C. and a pressure of 0.74 MPa at a pressure of 13 hPa or less by reducing the pressure for 30 seconds. Then, hot pressing was performed at 120° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board laminated with the resin sheet is placed in an oven at 100°C for 30 minutes under a temperature condition of 100°C, and then placed in an oven at 175°C under a temperature condition of 175°C. 30 minutes after the transfer, heat curing was performed to form an insulating layer.

(4) Formation of via holes From above the insulating layer and the support, a laser is irradiated from above the support using a CO ₂ laser processing machine "605GTWIII(-P)" manufactured by Mitsubishi Electric Corporation to form a grid pattern. A via hole with a top diameter (70 μm) was formed in the insulating layer on the conductor. The laser irradiation conditions were a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.39 mJ/shot, two shots, and burst mode (10 kHz).

(5) Step of Roughening Treatment The substrate was peeled off from the circuit board provided with the via holes, and desmear treatment was performed. As the desmear treatment, the following wet desmear treatment was performed.

Wet desmear treatment: Swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution ("Concentrate" manufactured by Atotech Japan)・ Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan, Sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(6) Process of forming a conductor layer (6-1) Electroless plating process In order to form a conductor layer on the surface of the circuit board, a plating process including the following steps 1 to 6 (using chemicals manufactured by Atotech Japan) copper plating step) was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
It was washed at 60° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
It was treated at 30° C. for 1 minute with a sulfuric acid-acid sodium peroxodisulfate aqueous solution.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
Pre. Dip Neoganth B (trade name) was used for 1 minute at room temperature.
4. Application of activator (application of Pd to the surface of the insulating layer)
Using Activator Neoganth 834 (trade name), it was treated at 35° C. for 5 minutes.
5. Reduction (reduction of Pd applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. (trade name) and treated at 30° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
Using a mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name), at 35 ° C. Treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(6-2) Electroplating Process Next, an electrolytic copper plating process was performed using a chemical solution manufactured by Atotech Japan Co., Ltd. under the condition that the via holes were filled with copper. After that, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm connected to the via hole and a circular conductor pattern with a diameter of 10 mm not connected to the lower layer conductor were used to form a 10 μm thick resist pattern on the surface of the insulating layer. Then, a conductor layer having lands and conductor patterns was formed. Annealing was then performed at 190° C. for 90 minutes. This substrate was used as substrate A for evaluation.

(Measurement of thickness of insulating layer between conductor layers)
The cross-section of the evaluation substrate A was observed using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology). Specifically, a cross section perpendicular to the surface of the conductor layer was cut out by FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, cross-sectional SEM images at five randomly selected locations were observed, and the average value was taken as the thickness of the insulating layer between the conductor layers.

(Evaluation of wet insulation reliability of insulating layer)
The circular conductor side with a diameter of 10 mm of the evaluation board A obtained above was used as a + electrode, and the grid conductor (copper) side of the inner layer circuit board connected to the land with a diameter of 1 mm was used as a - electrode. "PC422-R8D" manufactured by Hirayama Seisakusho Co., Ltd.) is used, and the insulation resistance value in humidity for 200 hours under the conditions of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application is measured with an electrochemical migration tester (manufactured by IMVCORATION Co., Ltd. "MIG8600B"). This measurement was performed 6 times, and when the wet resistance value of all 6 test pieces was 10 ⁸ Ω or more, it was evaluated as “◯”, and when even one of the test pieces was less than 10 ⁸ Ω, it was evaluated as “x”.

<Evaluation of amount of warpage>
The resin sheets prepared in Examples and Comparative Examples were used as glass cloth-based BT resin double-sided copper-clad laminates (copper foil thickness 18 μm, substrate thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Company, size 15 cm × 18 cm). ) with a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), remove the PET film, and then heat cure at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. It was placed on a flat surface and the amount of warpage was confirmed. The average value of the amount of warp in each of the four corners was evaluated as "◯" if it was less than 1 cm, "Δ" if it was 1 to 2 cm, and "x" if it was 2 cm or more.

[Synthesis Example 1]
<Production of Elastomer A>
A reaction vessel was charged with 69 g of bifunctional hydroxy-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g/eq.) and Ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu). (manufactured by Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the mixture became uniform, the temperature was raised to 50° C., and while stirring, 8 g of isophorone diisocyanate (IPDI, isocyanate group equivalent=113 g/eq., manufactured by Evonik Degussa Japan) was added and reacted for about 3 hours. Next, after cooling the reactant to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g/eq.) and 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. Then, the temperature was raised to 80° C. while 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. Confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reactant was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain an elastomer A having a butadiene structure and phenolic hydroxyl groups (50% by mass of non-volatile content). rice field. The number average molecular weight was 5,500.

[Synthesis Example 2]
<Production of Elastomer B>
A flask equipped with a stirrer, thermometer and condenser was charged with 292.09 g of ethyl diglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by Exxon Mobil) as solvents, and 100.1 g of diphenylmethane diisocyanate ( 0.4 mol) and 426.6 g (0.2 mol) of polybutadiene diol (hydroxyl value: 52.6 KOH-mg/g, molecular weight: 2133) were charged and reacted at 70°C for 4 hours. Then, 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 41.0 g ( 0.1 mol) was charged, the temperature was raised to 150° C. over 2 hours, and the reaction was allowed to proceed for 12 hours.

After the reaction, a transparent brown liquid was obtained, and a polyimide resin solution with a non-volatile content of 55% and a viscosity of 14 Pa·s (25° C.) was obtained. The obtained polyimide resin solution was applied to a KBr plate, and the infrared absorption spectrum of the sample after volatilizing the solvent component ^was measured. Absorption of the imide ring was confirmed at ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Also, absorption of urethane bonds was confirmed at 1540 cm ⁻¹ . Further, the amount of carbon dioxide gas generated with the progress of imidization was tracked by the change in the weight charged in the flask and found to be 8.8 g (0.2 mol). The functional group equivalent of the acid anhydride of ethylene glycol bisanhydrotrimellitate is 0.2 mol, the amount of carbon dioxide generated is also 0.2 mol, all the acid anhydride is used for imide formation, and the carboxylic acid It is concluded that no anhydride is present. As a result, 0.2 mol of the isocyanate groups are converted to imide bonds, and the remaining isocyanate groups form urethane bonds with the hydroxyl groups of polybutadiene diol and the phenolic hydroxyl groups in the nonylphenol novolac resin, thereby forming phenol novolac resins in the resin. It is concluded that a polyimide urethane resin having phenolic hydroxyl groups in the resin and some of the phenolic hydroxyl groups being modified with urethane bonds was obtained.

[Example 1]
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) 30 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical "630LSD", epoxy equivalent: 90 to 105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, elastomer A (solid content 50%, number average molecular weight: 5500) 300 parts, cresol novolak resin (DIC Corporation "KA-1163", Phenolic hydroxyl group equivalent: 118 g/eq) 12 parts, SO-C4 (spherical silica surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs, average particle size 1 μm)) 740 parts of the mixture and 35 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish.

[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) 30 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical "630LSD", epoxy equivalent: 90 to 105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, elastomer B 272 parts, cresol novolak resin (DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, 950 parts of SO-C4 (spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., average particle diameter 1 μm, manufactured by Admatechs)) and 45 parts of methyl ethyl ketone were mixed and stirred at high speed. A resin varnish was prepared by uniformly dispersing with a rotating mixer.

[Example 3]
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) 30 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical "630LSD", epoxy equivalent: 90 to 105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, elastomer B 272 parts, cresol novolak resin (DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, 1070 parts of SO-C4 (spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.; average particle diameter 1 μm, manufactured by Admatechs)) and 50 parts of methyl ethyl ketone were mixed and stirred at high speed. A resin varnish was prepared by uniformly dispersing with a rotating mixer.

[Comparative Example 1]
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) 40 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent: 288 g / eq) 61 parts, naphthalene type epoxy resin (DIC "HP4710", epoxy equivalent 160 to 180 g / eq) 20 parts, aminophenol type epoxy resin (Mitsubishi Chemical company "630LSD", epoxy equivalent: 90 to 105 g / eq) 13 parts, curing accelerator (Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, polyester resin (Unitika Co., Ltd., "UE3400") 40 parts, cresol novolac resin (DIC "KA-1163", phenolic hydroxyl equivalent: 118 g / eq) 30 parts, SO-C4 (aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573" ) and 40 parts of methyl ethyl ketone were mixed with 950 parts of spherical silica (manufactured by Admatechs, average particle size 1 μm) surface-treated with ) and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish.

[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) 40 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent: 288 g / eq) 61 parts, naphthalene type epoxy resin (DIC "HP4710", epoxy equivalent 160 to 180 g / eq) 20 parts, aminophenol type epoxy resin (Mitsubishi Chemical company "630LSD", epoxy equivalent: 90 to 105 g / eq) 13 parts, curing accelerator (Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, polyester resin (Unitika Co., Ltd., "UE3400") 40 parts, cresol novolac resin (DIC "KA-1163", phenolic hydroxyl equivalent: 118 g / eq) 30 parts, SO-C4 (aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573" ) and 30 parts of methyl ethyl ketone were mixed and uniformly dispersed in a high-speed rotating mixer to prepare a resin varnish.

[Comparative Example 3]
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) 31 parts, bisphenol A novolac type Epoxy resin (manufactured by Mitsubishi Chemical Corporation "157S70", epoxy equivalent: 200 to 220 g / eq) 23 parts, naphthalene type epoxy resin (DIC Corporation "HP4710", epoxy equivalent 160 to 180 g / eq) 20 parts, polyester resin (Unitika company, "UE3400") 4 parts, cresol novolak resin (DIC "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 24 parts, SO-C4 (aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated spherical silica (manufactured by Admatechs, average particle size 1 μm)) 640 parts, curing accelerator (manufactured by Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, and 30 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish.

Abbreviations and the like in the table below are as follows.
UE3400: Polyester resin, ZX1059 manufactured by Unitika: 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq, 630LSD manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.: aminophenol type Epoxy resin, epoxy equivalent: 90 to 105 g / eq, Mitsubishi Chemical Corporation NC3000H: biphenyl type epoxy resin, epoxy equivalent: 288 g / eq, Nippon Kayaku HP4710: naphthalene type epoxy resin, manufactured by DIC, epoxy equivalent 160 ~ 180g/eq
157S70: Bisphenol A novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq
SO-C4: Spherical silica (manufactured by Admatechs, average particle size 1 μm) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)
KA-1163: cresol novolac resin, phenolic hydroxyl equivalent: 118 g / eq, 1B2PZ manufactured by DIC: 1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd. Content of component (c): Non-volatile components of the resin composition It represents the content (% by mass) based on 100% by mass.
Content of component (a): The content (% by mass) when the non-volatile component of the resin composition excluding component (c) is taken as 100% by mass.

[Production example 1]
<Preparation of resin sheet for fan-out type WLP>
On a polyethylene terephthalate film (thickness 38 μm), the resin varnish described in Example 1 was applied with a die coater so that the thickness of the resin composition layer after drying was 200 μm. ° C.) for 10 minutes to obtain a resin sheet.

When the sealing layer of the fan-out type WLP shown in FIG. 3 was produced using the above resin sheet, it was found to have sufficient performance as a fan-out type WLP.

1 circuit board 10 substrate with wiring layer 11 substrate (core substrate)
12 First metal layer 13 Second metal layer 14 Wiring layer (embedded wiring layer)
20 resin sheet 21 resin composition layer 21' insulating layer 22 support 31 via hole 40 conductor layer 41 plating seed layer 42 electrolytic plating layer 61 filled via 100 semiconductor chip package 110 semiconductor chip 120 sealing layer 130 rewiring forming layer (insulating layer)
140 conductor layer (rewiring layer)
150 solder resist layer 160 bump

Claims (11)

The resin composition for forming a resin sheet having a support and a resin composition layer containing the resin composition provided on the support,
A resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler,
Component (a) is at least one selected from butadiene structural units, polysiloxane structural units, (meth)acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. has a structural unit of
Component (a) is one or more selected from resins having a glass transition temperature of 25°C or less and resins that are liquid at 25°C, or
The component (a) has a polystyrene equivalent number average molecular weight (Mn) of 1,000 to 1,000,000 measured using GPC (gel permeation chromatography),
(b1) component is a glycidylamine type epoxy resin, (b2) component is a biphenyl type epoxy resin,
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass,
The cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour has a relative dielectric constant of 3.5 or less at a measurement frequency of 5.8 GHz at 23 ° C., and a relative dielectric constant at a measurement frequency of 1 GHz at 23 ° C. A resin composition in which the difference from the ratio is 0.3 or less. The resin composition for forming a resin sheet having a support and a resin composition layer containing the resin composition provided on the support,
A resin composition containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler,
Component (a) is at least one selected from butadiene structural units, polysiloxane structural units, (meth)acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. has a structural unit of
Component (a) is one or more selected from resins having a glass transition temperature of 25°C or less and resins that are liquid at 25°C, or
The component (a) has a polystyrene equivalent number average molecular weight (Mn) of 1,000 to 1,000,000 measured using GPC (gel permeation chromatography),
(b1) component is a glycidylamine type epoxy resin, (b2) component is a biphenyl type epoxy resin,
The content of the component (c) is 50% by mass to 95% by mass when the non-volatile component of the resin composition is 100% by mass,
A cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour has a dielectric loss tangent at a measurement frequency of 5.8 GHz at 23 ° C. of 0.01 or less, and a dielectric loss tangent at a measurement frequency of 1 GHz at 23 ° C. of the cured product. difference is 0.002 or less, the resin composition. 3. The resin composition according to claim 1, wherein component (a) has a functional group capable of reacting with components (b1) and (b2). The resin composition according to any one of claims 1 to 3, wherein component (a) has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 4, further comprising (d) a curing agent, the curing agent being one or more selected from phenolic curing agents and active ester curing agents. . The resin composition according to any one of claims 1 to 5, which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 6 provided on the support. 8. The resin sheet according to claim 7, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 6. A semiconductor chip package comprising a semiconductor chip mounted on the circuit board according to claim 9 . A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of claims 1 to 6 or the resin sheet according to claim 7 or 8.

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