JP6947251B2 - Resin composition - Google Patents

Description

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

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

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

Japanese Unexamined Patent Publication No. 2015-82535

In recent years, there has been a demand for the production of smaller semiconductor packages, and the insulating layer used for the semiconductor package is required to be a thinner layer. Therefore, it is required that the insulation reliability is excellent, the occurrence of warpage is suppressed, and the coefficient of linear thermal expansion (CTE, sometimes referred to as the coefficient of thermal expansion) is low.

However, insulation reliability, warpage, and CTE are in a trade-off relationship, especially when the thickness of the insulating layer is thin, and at the same time, various designs of resin compositions that exhibit sufficient performance have been studied, but they continue. It was a problem to be solved.

The present invention has been made to solve the above problems, and is a resin composition capable of obtaining an insulating layer having excellent insulation reliability, suppression of warpage, and a low coefficient of linear thermal expansion; a resin using the same. The purpose of the present invention is to provide a sheet, a circuit board, and a semiconductor chip package.

The present inventors contain (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) a predetermined amount of an inorganic filler. Further, the cured product heat-cured at 180 ° C. for 1 hour has an elastic modulus of 18 GPa or less at 23 ° C., a specific dielectric constant of the cured product at a measurement frequency of 5.8 GHz at 23 ° C. of 3.5 or less, and 23 of the cured product. By satisfying the requirement that the difference from the specific dielectric constant of the measurement frequency of 1 GHz at ° C. is 0.3 or less, an insulating layer having excellent insulation reliability, suppression of warpage, and a low linear thermal expansion coefficient can be obtained. The present invention has been completed.

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 of the cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour at 23 ° C. is 18 GPa or less.
The relative permittivity of the cured product at a measurement frequency of 5.8 GHz at 23 ° C. is 3.5 or less, and the difference from the relative permittivity of the cured product at a measurement frequency of 1 GHz at 23 ° C. is 0.3 or less. Resin composition.
[2] The dielectric loss tangent of the cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour at a measurement frequency of 5.8 GHz at 23 ° C. is 0.01 or less, and the measured frequency of the cured product at 23 ° C. is 1 GHz. The resin composition according to [1], wherein the difference from the dielectric loss tangent is 0.002 or less.
[3] The content of the component (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass, [1] or [2]. The resin composition according to.
[4] The component (a) is selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of [1] to [3], which has one or more structural units.
[5] The composition according to any one of [1] to [4], wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. Resin composition.
[6] The resin composition according to any one of [1] to [5], wherein the component (a) has a functional group capable of reacting with the component (b1) and the component (b2).
[7] The resin composition according to any one of [1] to [6], wherein the component (a) has a phenolic hydroxyl group.
[8] The method according to any one of [1] to [7], further comprising (d) a curing agent, wherein the curing agent is one or more selected from a phenolic curing agent and an active ester curing agent. Resin composition.
[9] The resin composition according to any one of [1] to [8], which is a resin composition for an insulating layer of a semiconductor chip package.
[10] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [9].
[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 including an insulating layer formed of 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 containing the resin composition according to any one of [1] to [9] or a semiconductor chip sealed with the resin sheet according to [10].

According to the present invention, a resin composition capable of obtaining an insulating layer having excellent insulation reliability, suppression of warpage, and a low coefficient of linear thermal expansion; a resin sheet, a circuit board, and a semiconductor chip package using the same are provided. can do.

FIG. 1 is a schematic cross section showing an example of a step (3) of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers between layers in the method for manufacturing a circuit board of the present invention. It is a figure. FIG. 2 is a schematic cross section showing an example of the process (3) in the method for manufacturing a circuit board of the present invention, in which the step (3) is a step of polishing or grinding the insulating layer to expose the wiring layer and interconnecting the wiring layers. It is a figure. 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, the resin sheet, the circuit board, and the semiconductor chip package of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention 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. 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, and the resin composition is heat-cured at 180 ° C. for 1 hour. The cured product has an elastic coefficient of 18 GPa or less at 23 ° C., a specific dielectric constant of the cured product at a measurement frequency of 5.8 GHz at 23 ° C. is 3.5 or less, and the cured product has a measurement frequency of 1 GHz at 23 ° C. The difference from the specific dielectric constant of is 0.3 or less.

The resin composition contains a component (a), a component (b1), a component (b2), and a predetermined amount of the component (c), and the elastic modulus and relative permittivity of the cured product are within a predetermined range. Therefore, it is possible to obtain an insulating layer having excellent insulation reliability, suppressing the occurrence of warpage, and having 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. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Elastomer>
The resin composition comprises (a) an elastomer. In the present invention, the elastomer means a flexible resin, and is not particularly limited, but for example, in the molecule, a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, and an alkyleneoxy structural unit. , An isoprene structural unit, an isobutylene structural unit, and a resin that exhibits flexibility by having one or more structures selected from the polycarbonate structural unit. By containing a flexible resin such as the component (a), it is possible to obtain an insulating layer having excellent insulation reliability, suppressing the occurrence of warpage, and having a low coefficient of linear thermal expansion. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

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

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

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

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

The component (a) is not particularly limited as long as it is a flexible resin, but the component (b1) and the component (b2) described later (the component (b1) and the component (b2)) are collectively referred to as “component (b)”. It is preferable to have a functional group capable of reacting with.). The functional group that can react with the component (b) includes a functional group that appears by heating.

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

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

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

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

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

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

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

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

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50,000, more preferably 2500 to 30000.

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

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

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

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

Further, 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 content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

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

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

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

The content of the 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 the component (c) is 100% by mass from the viewpoint of imparting flexibility. Is 80% by mass or less, more preferably 75% by mass or less, and even more preferably 73% by mass or less. 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, still more preferably 55% by mass or more.

<(B1) Liquid epoxy resin having an aromatic structure and (b2) Solid epoxy resin having an aromatic structure>
The resin composition includes (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, may be simply referred to as “liquid epoxy resin”) refers to an epoxy resin having an aromatic structure that is liquid at a temperature of 20 ° C., and is contained in one molecule. It is preferable to have two or more epoxy groups in the resin. Further, (b2) a solid epoxy resin having an aromatic structure (hereinafter, may be simply referred to as “solid epoxy resin”) is an epoxy resin having an aromatic structure that is solid at a temperature of 20 ° C. It is preferable to have three or more epoxy groups in one molecule. Aromatic structures are chemical structures generally defined as aromatics, including polycyclic aromatics and aromatic heterocycles. In the present invention, by using the liquid epoxy resin and the solid epoxy resin in combination, the compatibility of the component (a) is improved, and a resin composition having excellent flexibility can be obtained.

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

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

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

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

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

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

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

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

When the content of the liquid epoxy resin is B1 (mass%) and the content of the solid epoxy resin is B2 (mass%), it is preferable to satisfy the relationship of B1> B2 from the viewpoint of adjusting the melt viscosity. 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. The upper limit of the difference (B1-B2) is not particularly limited, but may be usually 10% by mass or less, 5% by mass or less, or the like.

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

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

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

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

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

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

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

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

<(D) Hardener>
The resin composition may include (d) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (b), and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system curing agent. The curing agent may be used alone or in combination of two or more. The component (d) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent, and is preferably a phenol-based curing agent and an active ester-based curing agent. It is preferably one or more selected from the agents.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

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

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

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

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

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

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidendiphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which all of the triazine is converted into a trimer) and the like can be mentioned.

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

When the resin composition contains the 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, still more preferably 5% by mass. It is as follows. The lower limit is not particularly limited, but is preferably 1% by mass or more.

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

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

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

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

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

When the resin composition contains the component (e), the content of the curing accelerator in the resin composition is not particularly limited, but the total amount of the non-volatile components of the component (b) and the curing agent is 100% by mass. When this is done, 0.01% by mass to 3% by mass is preferable.

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

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

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, still more preferably. More preferably, it is 0.5% by mass to 10% by mass.

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

<Physical characteristics of resin composition>
The 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, and 13 GPa or less, 11 GPa or less, or 10 GPa or less. Is more preferable. The lower limit is not particularly limited, but may be, for example, 0.01 GPa or more, 0.5 GPa or more, 1 GPa or more, and the like. By setting the elastic modulus to 18 GPa or less, the occurrence of warpage of the cured product can be suppressed. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

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

The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 1 hour preferably has a relative permittivity of 3.6 or less and more preferably 3.5 or less at a measurement frequency of 1 GHz at 23 ° C. It is preferably 3.4 or less, and more preferably 3.4 or less. The lower limit is not particularly limited, but may be, for example, 1 or more, 1.1 or more, 1.2 or more, and the like. Within the above range, the CTE can be lowered and the occurrence of the amount of warpage can be suppressed. The relative permittivity can be measured according to the method described in <Measurement of relative permittivity and dielectric loss tangent> described later.

Further, the relative permittivity of the cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 1 hour at a measurement frequency of 5.8 GHz at 23 ° C. and the relative permittivity of the cured product at a measurement frequency of 1 GHz at 23 ° C. 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. Hereinafter, 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 may be, for example, 0 or more, 0.001 or more, and the like. Within the above range, it is possible to obtain an insulating layer having excellent insulation reliability, suppressing warpage, and having a low CTE. The difference in relative permittivity can be measured according to the method described in <Measurement of relative permittivity and dielectric loss tangent> described later.

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

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

The difference between the dielectric loss tangent of the cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 1 hour at a measurement frequency of 5.8 GHz at 23 ° C. and the dielectric loss tangent at a measurement frequency of 1 GHz at 23 ° C. of the cured product is 0. It is preferably .002 or less, more preferably 0.001 or less, and even more preferably 0.0005 or less. The lower limit is not particularly limited, but may be, for example, 0 or more. Within the above range, it is possible to provide an insulating layer capable of suppressing insertion loss to a low level. The difference in dielectric loss tangent can be measured according to the method described in <Measurement of Relative Permittivity and Dissipation Factor> described later.

The 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 a characteristic that the occurrence of warpage is suppressed. The size of the warp is preferably less than 2 cm, more preferably 1.5 cm or less, and more preferably 1 cm or less. The warp can be measured according to the method described in <Evaluation of the amount of warp> described later.

The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 1 hour has an insulation resistance value (wet insulation reliability) in wet condition for 200 hours under the condition of 130 ° C., 85% relative humidity, and 3.3 V DC voltage application. It shows the property that (sex) gives good results. The resistance value is preferably 10 ⁸ Ω or more, more preferably 10 ⁹ Ω or more, and further preferably 10 ¹⁰ Ω or more. The wet insulation reliability can be measured according to the method described in <Evaluation of wet insulation reliability> described later.

The coefficient of linear thermal expansion (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 lower, more preferably 15 ppm / ° C. or lower, from the viewpoint of suppressing warpage. More preferably, it is 10 ppm / ° C. or less. The lower limit is not particularly limited, but may be 1 ppm / ° C. or higher. The coefficient of linear thermal expansion can be measured according to the procedure of <Measurement of coefficient of linear thermal expansion (CTE)> described later.

Since the resin composition of the present invention has excellent insulation reliability, suppresses the occurrence of warpage, can provide an insulating layer having a low coefficient of linear thermal expansion, and contains components (b1) and (b2) ( a) The compatibility of the components is good. Therefore, the resin composition of the present invention forms an insulating layer of a resin composition (resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board) for forming an insulating layer of a semiconductor chip package. A resin composition (plating) for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board). It can be more preferably used as a resin composition for an interlayer insulating layer of a circuit board that forms a conductor layer).
It is also suitable as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring). Can be used.

[Resin sheet]
The resin sheet of the present invention 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.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

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

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

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

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

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

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

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

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

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

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

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

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

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

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

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

<Process (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. As an example shown in FIGS. 1 (A) and 2 (A), the base material 10 with a wiring layer has a first metal layer 12 and a second metal layer that are a part of the base material 11 on both sides of the base material 11. 13 are each provided, and the wiring layer 14 is provided on the surface of the second metal layer 13 opposite to the surface of the second metal layer 13 on the base material 11 side. For details, a dry film (photosensitive resist film) is laminated on a substrate and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. The developed pattern dry film is used as a plating mask to form a wiring layer by an electrolytic plating method, and then the pattern dry film is peeled off. Although FIGS. 1 and 2 have a first metal layer 12 and a second metal layer 13, the first metal layer 12 and the second metal layer 13 may not be provided.

Examples of the substrate include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. A metal layer such as copper foil may be formed on the surface. Further, as shown in FIGS. 1 (A) and 2 (A), the first metal layer 12 and the second metal layer 13 (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.) that can be peeled off from the surface are formed. , The trade name "Micro Tin") 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, a dry film such as a novolak resin or an acrylic resin can be used. A commercially available product may be used as the dry film.

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

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

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further preferably 5 /. It is 5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

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

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

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

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

<Process (2)>
The step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing the resin sheet to form an insulating layer. As an example shown in FIG. 1B, the wiring layer 14 of the base material with a 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 thermoset to form an insulating layer (reference numeral 21'in FIG. 1 (C) or FIG. 2 (B)). The resin sheet 20 is formed by laminating the resin composition layer 21 and the support 22 in this order.

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

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

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

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

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with a wiring layer and heat-cured. As shown in FIG. 2B, the resin sheet is placed on the base material with a wiring layer. The support may be peeled off before laminating. Further, the support may be peeled off before the roughening treatment step described later.

<Process (3)>
The step (3) is a step of connecting the wiring layers between layers. The details are a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers (see FIGS. 1C and 1D). Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers (see FIG. 2C).

When a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers is adopted, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, etc. can be mentioned. It is preferably done by. This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. For details, as shown in FIG. 1 (C) as an example, in the step (3), laser irradiation is performed from the surface side of the support 22, and the wiring layer 14 is passed through the support 22 and the insulating layer 21'. The via hole 31 to be exposed is formed.

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

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

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

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

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

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

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

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

When the step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed and the polished or ground surface can be exposed. As long as it is horizontal, a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a buff, or a surface grinding method by rotating a grindstone. And so on. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers between layers, a smear removing step and a roughening treatment step may be performed, or a conductor layer may be formed. Further, as shown in FIG. 2C as an example, it is not necessary to expose all the wiring layers 14, and a part of the wiring layers 14 may be exposed.

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

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

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

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

In another preferred embodiment, the semiconductor chip is reflowed and joined to the circuit board. The reflow condition can be, for example, in the range of 120 ° C. to 300 ° C.

It is also possible to obtain a semiconductor chip package by joining the semiconductor chip to a circuit board and then filling the semiconductor chip with a mold underfill material, for example. 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.

In the second aspect of the semiconductor chip package of the present invention, for example, in the semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 3, the sealing layer 120 is formed of the resin composition or resin of the present invention. It is a semiconductor chip package manufactured from sheets. The semiconductor chip package 100 is rewired on the surface of the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and the side opposite to the side covered by the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and bumps 160 are provided. The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and heat-curing to form a sealing layer.
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
It includes (F) a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

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

The material used for the base material is not particularly limited. As the base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); glass fiber impregnated with epoxy resin or the like and thermosetting (for example, FR-) 4 Substrate); Examples thereof include 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 the step (D) described later and the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

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

<Process (C)>
Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip or applying the resin composition of the present invention on a semiconductor chip and heat-curing it to form a sealing layer. be. In the step (C), it is preferable that the resin composition layer of the resin sheet of the present invention is laminated on the semiconductor chip and heat-cured to form a sealing layer.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Process (G)>
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, and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease of manufacturing a semiconductor chip package. .. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

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

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

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

A third aspect of the semiconductor chip package of the present invention includes, for example, a rewiring forming layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. 3 as an example. A semiconductor chip package manufactured from the resin composition or resin sheet of the present invention.

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

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

(Preparation of cured product for evaluation)
A glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works Co., Ltd.) on the release agent-treated PET film ("501010" manufactured by Lintec Corporation, thickness 38 μm, 240 mm square) treated with a mold release agent. , Thickness 0.7 mm, 255 mm square) and fixed on all four sides with polyimide adhesive tape (width 10 mm) (hereinafter, "fixed PET film").
PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). , Hereinafter referred to as "release PET") with a die coater so that the thickness of the resin composition layer after drying is 40 μm, and dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to resin. I got a sheet. Each resin sheet (thickness 40 μm, 200 mm square) is treated with a release agent for a PET film in which the resin composition layer is fixed using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials, CVP700). A resin sheet was obtained by laminating in the center so as to be in contact with the surface. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, under the temperature condition of 100 ° C., it was put into the oven at 100 ° C. for 30 minutes, and then at the temperature condition of 175 ° C., it was transferred to the oven at 175 ° C. and then thermoset for 30 minutes. Then, the substrate was taken out under a room temperature atmosphere, the release PET was peeled off from the resin sheet with a support, and then the substrate was further put into an oven at 190 ° C. and then heat-cured under curing conditions for 90 minutes.

After thermosetting, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth base material epoxy resin double-sided copper-clad laminate, and the PET film (Lintec Corporation "501010") is also peeled off to obtain a sheet-shaped cured product. rice field. The obtained cured product is referred to as an "evaluation cured product".

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

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

<Measurement of relative permittivity and dielectric loss tangent>
The resin varnishes obtained in Examples and Comparative Examples were placed on a release-treated PET film (“PET501010” manufactured by Lintec Corporation) with a die coater so that the thickness of the resin composition layer after drying was 40 μm. And dried at 80-110 ° C. (average 95 ° C.) for 6 minutes. Then, it was heat-treated at 180 ° C. for 1 hour and peeled off from the support to obtain a cured film. The cured film was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. For this evaluation sample, the relative permittivity at a measurement frequency of 1 GHz or 5.8 GHz and the dielectric loss tangent were measured at a measurement temperature of 23 ° C. using an HP8362B device manufactured by Agilent Technologies. The two test pieces were measured and the average value was calculated. Further, 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 is obtained, and the dielectric loss tangent (average value) at the measurement frequency of 1 GHz and the measurement frequency 5. The difference from the dielectric loss tangent (average value) of 8 GHz was calculated.

<Evaluation of wet insulation reliability>
(Preparation of evaluation board)
(1) Base treatment of inner layer circuit board Glass cloth base material epoxy resin double-sided copper having circuit conductors (copper) formed on both sides as an inner layer circuit board with a wiring pattern of 1 mm square lattice (remaining copper ratio is 70%). A stretched laminated board (copper foil thickness 18 μm, substrate thickness 0.3 mm, “R1515F” manufactured by Panasonic) was prepared. Both sides of the inner layer circuit board were immersed in "CZ8100" manufactured by MEC to roughen the copper surface (copper etching amount 0.7 μm).

(2) Laminating of resin sheets PET film ("Lumilar R80" manufactured by Toray Industries, Inc.) in which each resin varnish produced in Examples and Comparative Examples was released with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Co., Ltd.). , Thickness 38 μm, softening point 130 ° C., hereinafter “release PET”), coated with a die coater so that the thickness of the resin composition layer after drying is 35 μm, and 80 ° C. to 120 ° C. (average 100 ° C.). The resin sheet was obtained by drying at (° C.) for 10 minutes. Using a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700), the prepared resin sheet is used on both sides of the inner layer circuit board so that the resin composition layer is in contact with the inner layer circuit board. Laminated in. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat 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 on which the resin sheet is laminated is placed in an oven at 100 ° C. for 30 minutes, and then in an oven at 175 ° C. under temperature conditions of 175 ° C. After transferring to, it was heat-cured for 30 minutes 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 machine "605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation to create a lattice pattern.} A via hole having 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, a number of shots of 2, and a burst mode (10 kHz).

(5) Step of roughening treatment The support was peeled off from the circuit board provided with the via hole, and desmear treatment was performed. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment: A swelling solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, followed by an oxidizing agent solution (Atotech Japan's "Concentrate"・ 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 (Atotech Japan's“ Reduction Solution Securigant P ”, It was immersed in a sulfuric acid aqueous solution) at 40 ° C. for 5 minutes and then dried at 80 ° C. for 15 minutes.

(6) Step of forming a conductor layer (6-1) Electroplating-free plating step In order to form a conductor layer on the surface of the circuit board, a plating step including the following steps 1 to 6 (using a chemical solution manufactured by Atotech Japan). The conductor layer was formed by performing the copper plating step).

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

(6-2) Electrolytic Plating Step Next, an electrolytic copper plating step was performed under the condition that the via hole was filled with copper using a chemical solution manufactured by Atotech Japan. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted through the via hole and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor were used, and the thickness of 10 μm was applied to the surface of the insulating layer. A conductor layer with lands and conductor patterns was formed. Next, the annealing treatment was performed at 190 ° C. for 90 minutes. This substrate was designated as the evaluation substrate A.

(Measurement of thickness of insulating layer between conductor layers)
A cross section of the evaluation substrate A was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). Specifically, a cross section in a direction perpendicular to the surface of the conductor layer was cut out by a FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross section SEM image. For each sample, five randomly selected cross-sectional SEM images 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)
An advanced accelerated life test device (with the circular conductor side of the evaluation substrate A obtained above having a diameter of 10 mm as a + electrode and the lattice conductor (copper) side of the inner layer circuit board connected to the land having a diameter of 1 mm as a-electrode). Using "PC422-R8D" manufactured by Hirayama Seisakusho Co., Ltd., the insulation resistance value in wet condition for 200 hours under the condition of 130 ° C., 85% relative humidity, and 3.3V DC voltage application was measured by the electrochemical migration tester (IMV CORPORATION "IMV CORPORATION". It was measured with MIG8600B ”). This measurement is performed six times, "○" and when the middle resistance value humidity of more than 10 ⁸ Omega in all test pieces of 6 points, if less than even one 10 ⁸ Omega was "×".

<Evaluation of warpage amount>
The resin sheet produced in Examples and Comparative Examples was used as a glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company's “HL832NSF LCA”, size 15 cm × 18 cm. ) With a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and after removing the PET film, heat-cured at 100 ° C for 30 minutes and then at 180 ° C for 30 minutes. The resin was placed on a flat surface and the amount of warpage was confirmed. The average value of the amount of warpage of each of the four corners was "○" when it was less than 1 cm, "Δ" when it was 1 to 2 cm, and "x" when it was 2 cm or more.

[Synthesis Example 1]
<Manufacturing of Elastomer A>
In a reaction vessel, 69 g of bifunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) And Ipsol 150 (aromatic hydrocarbon mixed solvent: Idemitsu). 40 g (manufactured by Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product was cooled to room temperature, and then 23 g of a cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyldiglycol acetate (manufactured by Daicel) were added thereto. Then, the temperature was raised to 80 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. The confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain an elastomer A (nonvolatile content 50% by mass) having a butadiene structure and a phenolic hydroxyl group. rice field. The number average molecular weight was 5500.

[Synthesis Example 2]
<Manufacturing of elastomer B>
In a flask equipped with a stirrer, a thermometer and a condenser, 292.09 g of ethyldiglycol acetate and 292.09 g of Solbesso 150 (aromatic solvent, manufactured by Exxon Mobile Co., Ltd.) were charged as solvents, and 100.1 g of diphenylmethane diisocyanate (100.1 g). 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. Next, nonylphenol novolak resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) 195.9 g (0.2 mol) and ethylene glycol bisamhydrotrimerite 41.0 g ( 0.1 mol) was charged, the temperature was raised to 150 ° C. over 2 hours, and the reaction was carried out for 12 hours.

After the reaction, it became a transparent brown liquid, and a polyimide resin solution having a non-volatile content of 55% and a viscosity of 14 Pa · s (25 ° C.) was obtained. The obtained solution of the polyimide resin was coated on a KBr plate, the results of measuring the infrared absorption spectrum of the sample after evaporation of the solvent component, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group have disappeared completely, 725 cm Absorption of the imide ring was confirmed at ^-1 and 1780 cm ^-1 and 1720 cm ^-1. Absorption of urethane bonds was confirmed at 1540 cm- ^1. The amount of carbon dioxide generated with the progress of imidization was 8.8 g (0.2 mol), which was tracked by the change in the weight charged in the flask. The functional group equivalent of the acid anhydride of ethylene glycol bisanhydrotrimeritate is 0.2 mol, the amount of carbon dioxide gas generated is also 0.2 mol, all the acid anhydrides are used for imide formation, and the carboxylic acid. It is concluded that the anhydride is not present. As a result, 0.2 mol of the isocyanate groups are converted into imide bonds, and the remaining isocyanate groups form urethane bonds together with the hydroxyl groups of the polybutadienediol and the phenolic hydroxyl groups in the nonylphenol novolac resin, whereby phenol novolac is formed in the resin. It is concluded that a polyimide urethane resin having a phenolic hydroxyl group of the resin and having some phenolic hydroxyl groups modified by a urethane bond was obtained.

[Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 30 parts, biphenyl type epoxy resin (Nippon Kayakusha "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630 LSD", epoxy equivalent: 90-105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, Epoxy A (solid content 50%, number average molecular weight: 5500) 300 parts, cresol novolac resin (DIC Co., Ltd. "KA-1163", Twelve parts of phenolic hydroxyl group equivalent: 118 g / eq), spherical silica surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (Admatex Co., Ltd., average particle size 1 μm)) 740 parts and 35 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 2]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 30 parts, biphenyl type epoxy resin (Nippon Kayakusha "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630 LSD", epoxy equivalent: 90-105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, elastomer B 272 parts, cresol novolac resin (DIC company "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, 950 parts of spherical silica (manufactured by Admatex, average particle size 1 μm) surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) and 45 parts of methyl ethyl ketone are mixed and high-speed. A resin varnish was prepared by uniformly dispersing it with a rotary mixer.

[Example 3]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 30 parts, biphenyl type epoxy resin (Nippon Kayakusha "NC3000H", epoxy equivalent: 288 g / eq) 8 parts, aminophenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "630 LSD", epoxy equivalent: 90-105 g / eq) 5 parts, curing accelerator ( Shikoku Kasei Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole) 1 part, elastomer B 272 parts, cresol novolac resin (DIC company "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 12 parts, 1070 parts of spherical silica (manufactured by Admatex, average particle size 1 μm) surface-treated with SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) and 50 parts of methyl ethyl ketone are mixed and high-speed. A resin varnish was prepared by uniformly dispersing it with a rotary mixer.

[Comparative Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq) 40 parts, biphenyl type epoxy resin (Nippon Kayakusha "NC3000H", epoxy equivalent: 288 g / eq) 61 parts, naphthalene type epoxy resin (DIC company "HP4710", epoxy equivalent 160-180 g / eq) 20 parts, aminophenol type epoxy resin (Mitsubishi) "630LSD" manufactured by Kagaku Co., Ltd., epoxy equivalent: 90 to 105 g / eq) 13 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, polyester resin (manufactured by Unitica, "UE3400") 40 parts, cresol novolac resin ("KA-1163" manufactured by DIC, phenolic hydroxyl group equivalent: 118 g / eq) 30 parts, SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.) ) 950 parts of spherical silica (manufactured by Admatex Co., Ltd., average particle size 1 μm)) and 40 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 2]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1: 1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq) 40 parts, biphenyl type epoxy resin (Nippon Kayakusha "NC3000H", epoxy equivalent: 288 g / eq) 61 parts, naphthalene type epoxy resin (DIC company "HP4710", epoxy equivalent 160-180 g / eq) 20 parts, aminophenol type epoxy resin (Mitsubishi) "630LSD" manufactured by Kagaku Co., Ltd., epoxy equivalent: 90 to 105 g / eq) 13 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, polyester resin (manufactured by Unitica, "UE3400") 40 parts, cresol novolac resin ("KA-1163" manufactured by DIC, phenolic hydroxyl group equivalent: 118 g / eq) 30 parts, SO-C4 (aminosilane coupling agent ("KBM573" manufactured by Shinetsu Chemical Industry Co., Ltd.) ), 200 parts of spherical silica (manufactured by Admatex Co., Ltd., average particle size 1 μm)) and 30 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 3]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation, 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 31 parts, bisphenol A novolak type 23 parts of epoxy resin ("157S70" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 200 to 220 g / eq), 20 parts of naphthalene type epoxy resin ("HP4710" manufactured by DIC, epoxy equivalent: 160 to 180 g / eq), polyester resin (Unitica) 4 parts of "UE3400" manufactured by cresol novolac resin ("KA-1163" manufactured by DIC, 24 parts of phenolic hydroxyl group equivalent: 118 g / eq), SO-C4 (aminosilane coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd.)) 640 parts of spherical silica (manufactured by Admatex, average particle size 1 μm) surface-treated with “KBM573”), 1 part of curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), And 30 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

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

[Production Example 1]
<Manufacturing of resin sheet for Fan-out type WLP>
The resin varnish described in Example 1 was applied on a polyethylene terephthalate film (thickness 38 μm) with a die coater so that the thickness of the resin composition layer after drying was 200 μm, and the temperature was 80 to 120 ° C. (average 100). The resin sheet was obtained by drying at (° C.) for 10 minutes.

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

1 Circuit board 10 Base material with wiring layer 11 Base material (core board)
12 1st metal layer 13 2nd metal layer 14 Wiring layer (embedded wiring layer)
20 Resin sheet 21 Resin composition layer 21'Insulation layer 22 Support 31 Via hole 40 Conductor layer 41 Plating seed layer 42 Electroplating layer 61 Field via 100 Semiconductor chip package 110 Semiconductor chip 120 Sealing layer 130 Rewiring formation layer (insulation layer)
140 Conductor layer (rewiring layer)
150 solder resist layer 160 bumps

Claims (9)

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 (a) is 30% by mass to 85% by mass when the non-volatile component of the resin composition excluding the component (c) is 100% by mass.
Component (a) has a butadiene structure Unit,
(A) component state, and are 1 or more glass transition temperatures which are selected from the resin is 25 ° C. or less of the resin, and liquid at 25 ° C.,
The component (a) has a functional group capable of reacting with the component (b1) and the component (b2).
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 dielectric loss tangent of the cured product obtained by thermosetting the resin composition at 180 ° C. for 1 hour at a measurement frequency of 5.8 GHz at 23 ° C. is 0.01 or less, and the dielectric loss tangent at a measurement frequency of 1 GHz at 23 ° C. of the cured product. Resin composition having a difference of 0.002 or less. The resin composition according to claim 1, wherein the component (a) has a phenolic hydroxyl group. The resin composition according to claim 1 or 2 , further comprising (d) a curing agent, wherein the curing agent is one or more selected from a phenolic curing agent and an active ester curing agent. The resin composition according to any one of claims 1 to 3 , which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 4. The resin sheet according to claim 5 , which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 4. A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to claim 7. A semiconductor chip package comprising the resin composition according to any one of claims 1 to 4 or a semiconductor chip sealed with the resin sheet according to claim 5 or 6.

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