TW201821525A - Resin compositions - Google Patents

Abstract

Provided are a resin composition which is excellent in insulation reliability, suppresses occurrence of bending and has low coefficient of linear thermal expansion, and a resin sheet, a circuit board and a semiconductor chip package using the resin composition. The resin composition of the present invention contains (a) an elastic polymer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) an inorganic filler, in which an amount of the component (c) contained in the resin composition is 50 to 95 mass% when nonvolatile components of the resin composition are 100 mass%, a cured product obtained by thermally curing the resin composition at 180 DEG C for one hour has an elastic modulus of 18 GPa or less at 23 DEG C, the cure product has 3.5 or less of a relative dielectric constant of a measured frequency 5.8 GHz at 23 DEG C, and a difference between the relative dielectric constant of the cure product and a relative dielectric constant of a measured frequency 1 GHz at 23 DEG C is 0.3 or less.

Description

   Resin composition   

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

In recent years, demand for small, high-performance electronic devices such as smart phones and tablet devices has increased. Along with this, there has been a higher demand for insulating materials (insulating layers) for semiconductor packages used in these small electronic devices. Functional.

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

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2015-82535

In recent years, the manufacture of smaller semiconductor packages has been required, and the insulating layers used in semiconductor packages have been required to be set to thinner layers. Therefore, it is required to have excellent insulation reliability, to suppress the occurrence of warpage, and to have a low coefficient of thermal expansion (CTE, sometimes referred to as a thermal expansion coefficient).

However, especially when the thickness of the insulation layer is thin, insulation reliability, warpage, and CTE may be trade-off relationships. Although various resin composition designs have been reviewed, But it is a problem that should be solved one after another.

The present invention is an invention completed to solve the above-mentioned problems, in order to provide a resin composition which can obtain an insulating layer having excellent insulation reliability, which can suppress the occurrence of warpage, and has a low coefficient of linear thermal expansion, and provides the use of the resin composition. The resulting resin sheet, circuit board, and semiconductor wafer package.

The inventors have found that by containing (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and a specified amount of (c) inorganic The filling material further satisfies the following requirements: the elastic modulus of the cured product obtained by heat curing at 180 ° C for 1 hour at 23 ° C is 18 GPa or less, and the specific dielectric constant of the cured product at 23 ° C and a measurement frequency of 5.8 GHz is 3.5 or less The difference between the specific permittivity of the hardened material at 23 ° C. and the measurement frequency of 1 GHz is 0.3 or less, an insulating layer having excellent insulation reliability, which can suppress the occurrence of warpage, and a low coefficient of linear thermal expansion can be obtained. .

That is, the present invention includes the following.

[1]. A resin composition comprising (a) an elastomer, (b1) a liquid epoxy resin having an aromatic structure, (b2) a solid epoxy resin having an aromatic structure, and (c) The resin composition of an inorganic filler is characterized in that when the non-volatile content of the resin composition is set to 100% by mass, the content of the component (c) is 50% to 95% by mass, and the resin composition is heated at 180 ° C. The elasticity of the hardened product obtained at 1 hour after hardening is 23 GPa or less at 23 ° C. The specific permittivity of the hardened material at 23 ° C and the measurement frequency of 5.8GHz is 3.5 or less, and the hardened product is at 23 ° C and the measurement frequency is 1GHz. The difference in specific permittivity is 0.3 or less.

[2]. The resin composition according to the above [1], wherein the dielectric tangent of the hardened product obtained by heat curing the resin composition at 180 ° C for 1 hour at 23 ° C and a measurement frequency of 5.8GHz is 0.01 or less, and The difference between the dielectric tangents of this cured product at 23 ° C. and a measurement frequency of 1 GHz is 0.002 or less.

[3]. The resin composition as described in [1] or [2] above, wherein when the non-volatile content of the resin composition after removing the component (c) is set to 100% by mass, the content of the component (a) is 30 Mass% ~ 85 mass%.

[4]. The resin composition according to any one of the above [1] to [3], wherein the component (a) has a structure selected from a butadiene structural unit, a polysiloxane structural unit, and a (meth) acrylate One or more types of structural units, such as structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units.

[5]. The resin composition according to any one of the above [1] to [4], wherein the component (a) is selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin in a liquid state at 25 ° C. More than one.

[6]. The resin composition according to any one of the above [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 the above [1] to [6], wherein the component (a) has a phenolic hydroxyl group.

[8]. The resin composition according to any one of the above [1] to [7], further comprising (d) a hardener selected from the group consisting of phenol-based hardener and active ester hardener 1 More than that.

[9]. The resin composition according to any one of [1] to [8] above, which is a resin composition for an insulating layer of a semiconductor wafer package.

[10] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [9].

[11]. The resin sheet as described in [10] above, which is a resin sheet for an insulating layer of a semiconductor wafer package.

[12]. A circuit board characterized by comprising an insulating layer formed of a hardened body of the resin composition according to any one of [1] to [9].

[13]. A semiconductor chip package, characterized in that a semiconductor chip is mounted on the circuit substrate of the aforementioned [12].

[14]. A semiconductor wafer package comprising a semiconductor wafer sealed with the resin composition according to any one of [1] to [9], or the resin sheet described in [10].

According to the present invention, it is possible to provide a resin composition which can obtain an insulating layer having excellent insulation reliability, which can suppress the occurrence of warpage, and has a low coefficient of linear thermal expansion, and which can provide a resin sheet and a circuit board using the resin composition. , And semiconductor chip packaging.

1‧‧‧circuit board

10‧‧‧ Substrate with wiring layer

11‧‧‧ substrate (core substrate)

12‧‧‧ first metal layer

13‧‧‧Second metal layer

14‧‧‧Wiring layer (Buried wiring layer)

20‧‧‧ resin sheet

21‧‧‧ resin composition layer

21’‧‧‧ insulating layer

22‧‧‧ support

31‧‧‧through hole

40‧‧‧conductor layer

41‧‧‧plating seed layer

42‧‧‧ electrolytic plating

61‧‧‧Filling holes

100‧‧‧ semiconductor chip package

110‧‧‧Semiconductor wafer

120‧‧‧Sealing layer

130‧‧‧ redistribution forming layer (insulating layer)

140‧‧‧conductor layer (rewiring layer)

150‧‧‧solder resist layer

160‧‧‧ bump

[Fig. 1] Fig. 1 is a schematic diagram showing an example of a step of forming a through-hole in an insulating layer, forming a conductor layer, and performing an interlayer connection of a wiring layer in the method of manufacturing a circuit board of the present invention. Sectional view.

[Fig. 2] Fig. 2 shows an example of the step of grinding or grinding the insulating layer in step (3), exposing the wiring layer, and performing interconnection between the wiring layers in the method for manufacturing a circuit board of the present invention. Schematic cross-sectional view.

[FIG. 3] FIG. 3 is a schematic cross-sectional view showing an example of a semiconductor wafer package (Fan-out WLP) of the present invention.

    [Best Mode for Implementing Invention]    

Hereinafter, the resin composition, resin sheet, circuit board, and semiconductor wafer 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. When the non-volatile content of the resin composition is 100% by mass, the content of the component (c) is 50% to 95% by mass, and the resin composition is obtained by heat curing the resin composition at 180 ° C for 1 hour. The elastic modulus of the cured product at 23 ° C is 18 GPa or less. The specific permittivity of the cured product at 23 ° C and a measurement frequency of 5.8 GHz is 3.5 or less. The difference is 0.3 or less.

The component (a), the component (b1), the component (b2), and the specified amount of the component (c) are contained in the resin composition, and the elastic modulus and specific permittivity of the hardened material are set to a specified range. In this case, an insulating layer having excellent insulation reliability, suppressing occurrence of warpage, and having a low coefficient of linear thermal expansion can be obtained. If necessary, the resin composition may further include (d) a curing agent, (e) a curing accelerator, and (f) a flame retardant. Hereinafter, each component contained in a resin composition is demonstrated in detail.

    <(a) Elastomer>    

The resin composition contains (a) an elastomer. The term "elastomer" in the present invention means a resin having flexibility, and it is not particularly limited. For example, the elastomer has a molecule selected from a butadiene structural unit, a polysiloxane structural unit, and a (meth) acrylate. One or more structures of the structural unit, the alkylene structural unit, the alkyleneoxy structural unit, the isoprene structural unit, the isobutylene structural unit, and the polycarbonate structural unit are displayed. Out of soft resin. By including a soft resin such as the component (a), an insulating layer having excellent insulation reliability, suppressing the occurrence of warpage, and having a low coefficient of linear thermal expansion can be obtained. The "(meth) acrylate" refers to methacrylate and acrylate. The so-called structural unit means a structure obtained by removing one or two hydrogen atoms from a compound.

More specifically, the (a) component has a butadiene structural unit selected from polybutadiene and hydrogenated polybutadiene, a polysiloxane structural unit such as silicone rubber, and (meth) acrylate Structural units, alkylene structural units (preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), alkylene oxide structural units (preferably 2 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), isoprene structural unit, isobutylene structural unit, and polycarbonate structural unit Or two or more types of structural units are preferred; it has a structure selected from butadiene structural units, polysiloxane structural units, (meth) acrylate structural units, isoprene structural units, isobutylene structural units, or poly One or two or more structural units of the carbonate structural unit are more preferred; a structural unit having one or more selected from a butadiene structural unit and a (meth) acrylate structural unit is more preferred.

In order to exhibit flexibility, the component (a) is preferably a high molecular weight, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, and more preferably 5,000 to 9,00,000. The number average molecular weight (Mn) is a number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

In order to show flexibility, 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 which is liquid at 25 ° C.

The glass transition temperature (Tg) of the resin is 25 ° C or lower, preferably 20 ° C or lower, and more preferably 15 ° C or lower. The lower limit of the glass transition temperature is not particularly limited, but is usually -15 ° C or higher. The resin that is liquid at 25 ° C is preferably a resin that is liquid at 20 ° C or lower, and is 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 soft resin, but it has components (b1) and (b2) which can be described later (hereinafter, the components (b1) and (b2) are collectively referred to as "( b) Ingredients) The functional group that performs the reaction is preferred. The functional group that can react with the component (b) also includes a functional group that is visualized by heating.

In a suitable embodiment, the functional group capable of reacting with the component (b) is selected from the group consisting of a hydroxyl group (also preferably a phenolic hydroxyl group), a carboxyl group, an acid anhydride group, an epoxy group, an isocyanate group, and a urethane. One or more kinds of functional groups in a group of radicals. Among these, as the functional group, a hydroxyl group, an acid anhydride group, an epoxy group, and an isocyanate group are preferable, and a hydroxyl 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 suitable embodiment of the component (a) is a butadiene resin. As the butadiene resin, a butadiene resin in a liquid state at 25 ° C or a glass transition temperature of 25 ° C or lower is preferred, and is selected from a resin containing a hydrogenated polybutadiene skeleton (for example, a hydrogenated polybutadiene). Skeleton epoxy resin), hydroxyl-containing butadiene resin (also preferably phenolic hydroxyl-containing butadiene resin), carboxyl-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy resin One or more types of resins based on a group of butadiene resins based on isocyanate groups, butadiene resins containing isocyanate groups, and butadiene resins containing urethane groups are more preferred. Here, the so-called "butadiene resin" refers to a resin containing a butadiene structure, and the butadiene structure in such resins may be included in a main chain or a side chain. Part of or all of the butadiene structure can be hydrogenated. Here, the "resin containing a hydrogenated polybutadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessary that all of the polybutadiene skeleton is a 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, still more preferably 7,500 to 30,000, and even more preferably 10,000 to 15,000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10,000, and more preferably 200 to 5000. The term "functional group equivalent" means the number of grams of a resin containing 1 gram equivalent of a functional group. For example, the epoxy group equivalent can be measured in accordance with JIS K7236. The hydroxyl equivalent can be calculated by dividing the hydroxyl value measured by JIS K1557-1 by the molecular weight of KOH.

Specific examples of the butadiene resin include "Ricon 657" (epoxy-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon" 131MA5 '', `` Ricon 131MA10 '', `` Ricon 131MA17 '', `` Ricon 131MA20 '', `` Ricon 184MA6 '' (polybutadiene containing acid anhydride groups), `` JP-100 '', `` JP-200 '' (made by Soda Corporation) Epoxidized polybutadiene), "GQ-1000" (hydroxyl- and carboxyl-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both-terminal hydroxypolybutadiene) , "GI-1000", "GI-2000", "GI-3000" (both ends of hydrogenated polybutadiene), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin) made by DAICEL "EPOFRIEND A1005", "EPOFRIEND A1010", "EPOFRIEND A1020" (epoxide of styrene and butadiene and styrene block copolymer), "FCA-061L" (hydrogenated polybutadiene) manufactured by Nagasechemtex Skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin), etc.

As another suitable embodiment of the component (a), a linear polyimide obtained by using hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride as raw materials (Japanese Patent Application Laid-Open No. 2006- Polyimide described in Gazette 37083, International Publication No. 2008/153208). The content ratio of the butadiene structure of the polyfluoreneimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyfluoreneimide resin, refer to Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208, which are incorporated into the description of this specification.

Another suitable 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 preferred. The acrylic resin is selected from the group consisting of a hydroxyl-containing acrylic resin (also preferably a phenolic hydroxyl-containing acrylic resin), a carboxyl-containing acrylic resin, One or more types of resins composed of an acrylic resin containing an acid anhydride group, an acrylic resin containing an epoxy group, an acrylic resin containing an isocyanate group, and an acrylic resin containing a urethane group are more preferable. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and the (meth) acrylate structure in these resins may be included in the main chain or may be included in the side chain.

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

When the acrylic resin has a functional group, the functional group equivalent is preferably 1,000 to 50,000, and more preferably 2500 to 30,000.

Specific examples of the acrylic resin include Teisanresin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (containing carboxyl group) manufactured by Nagasechemtex Corporation. Acrylate copolymer resin, acid value 5 ~ 34mgKOH / g, weight average molecular weight 400,000 ~ 900,000, Tg-30 ~ 5 ℃), "SG-80H", "SG-80H-3", "SG-P3" (Epoxy-containing acrylate 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" (containing hydroxyl groups Acrylate copolymer resin, hydroxyl value of 20 ~ 40mgKOH / g, weight average molecular weight of 500,000 ~ 1.2 million, Tg-37 ~ -32 ℃), "ME-2000", "W-116.3" (manufactured by Gensang Kogyo Co., Ltd.) Carboxyl-containing acrylate copolymer resin), "W-197C" (hydroxy-containing acrylate copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylate copolymer resin), etc. .

A suitable embodiment of the component (a) is a carbonate resin. The carbonate resin is preferably a carbonate resin having a glass transition temperature of 25 ° C. or lower, and is selected from the group consisting of a hydroxyl group-containing carbonate resin (also preferably a phenolic hydroxyl group-containing carbonate resin) and a carboxyl group-containing carbonate. Resins, carbonate resins containing acid anhydride groups, carbonate resins containing epoxy groups, carbonate resins containing isocyanate groups, and carbonate resins containing urethane groups are more than one type of resin. good. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and among these resins, the carbonate structure may be included in a main chain or a 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 preferred ranges are also the same.

Specific examples of the carbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090", and "C-20" manufactured by Kuraray. -3090 "(polycarbonate diol) and the like.

In addition, a linear polyfluorene imine obtained by using a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a quaternary acid anhydride as raw materials (International Publication No. 2016/129541) can also be used. The content of the carbonate structure of the polyfluoreneimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyfluorene resin, refer to the description of International Publication No. 2016/129541, which is incorporated into the description of this specification.

A suitable embodiment of the component (a) is a polysiloxane resin, an alkylene resin, an alkylene oxide resin, an isoprene resin, or an isobutylene resin.

Specific examples of the polysiloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicones, and amine-terminated polysiloxane and tetrabasic acid anhydride as raw materials. The obtained linear polyfluorene imide (International Publication No. 2010/053185) and the like. Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray Corporation. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. Wait.

Specific examples of the alkoxy resin include "YX-7180" (resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation.

Moreover, as a suitable embodiment of another (a) component, acrylic rubber particles, polyamide fine particles, polysiloxane particles, etc. are mentioned. As specific examples of the acrylic rubber particles, a resin having a rubber elasticity, such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber, may be chemically cross-linked to make it insoluble and insoluble in organic solvents. Specific examples of the resin microparticles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Sterophildo AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (the above are manufactured by Gantsu Kasei Corporation), Paraloid EXL2655, EXL2602 (above (Made by Wu Yu Chemical Industry Co.). Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, and for example, those having a soft skeleton such as polyamidamine and imine, and specifically, VESTOSINT 2070 (Daicel-Huls) System), or SP500 (manufactured by Toray).

The content of the component (a) in the resin composition is preferably 85% by mass when the non-volatile content of the resin composition after removing the component (c) is set to 100% by mass in terms of imparting flexibility. Hereinafter, it is more preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 73% by mass or less. The lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, more preferably 45% by mass or more, and 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) Liquid epoxy resin with an aromatic structure (hereinafter referred to as "liquid epoxy resin") refers to an epoxy resin with an aromatic structure that is liquid at a temperature of 20 ° C. It is preferable to have two or more epoxy groups in one molecule. (B2) A solid epoxy resin having an aromatic structure (hereinafter 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. The so-called aromatic structure is generally defined as an aromatic chemical structure, and also includes 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.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, and glycidyl ester type epoxy resin having an aromatic structure are used. Glycidylamine type epoxy resin with aromatic structure, phenol novolac type epoxy resin, alicyclic epoxy resin with ester structure containing aromatic structure, cyclohexanedimethanol type ring with aromatic structure Oxygen resin and epoxy resin with butadiene structure containing aromatic structure are preferred; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin Resin is more preferred; bisphenol A epoxy resin and bisphenol F epoxy resin are more preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) made by DIC, "828US", "jER828EL" (double Phenol A type epoxy resin), "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (aminophenol type Epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and "EX-721" (glycidyl ester) manufactured by Nagasechemtex Type epoxy resin), "CELOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by DAICEL, "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl) manufactured by Nippon Steel Chemical Co., Ltd. Cyclohexane). These systems can be used singly or in combination of two or more.

The content of the liquid epoxy resin in the resin composition is preferably 1% by mass or more when the nonvolatile content in the resin composition is set to 100% by mass from the viewpoint of improving the compatibility of the component (a). It is more preferably 2% by mass or more, and 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 can be obtained, but it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

The epoxy equivalent of the liquid epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By setting it as this range, the crosslinking density of the hardened | cured material of a resin composition will be sufficient, and when a hardened | cured material is used as an insulating layer, an insulating layer with small surface roughness can be obtained. The epoxy equivalent of a liquid epoxy resin can be measured in accordance with JIS K7236, and refers to the mass of a resin containing 1 equivalent of an epoxy group.

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

As the solid epoxy resin, a naphthalene type 4-functional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin having an aromatic structure, a triphenol type epoxy resin, and a naphthol type ring are used. Oxygen resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF epoxy resin, and tetraphenylethane epoxy resin are Preferred; Naphthalene-type 4-functional epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin, and naphthyl ether-type epoxy resin are further preferred; naphthalene-type 4-functional epoxy resin, and The naphthyl ether type epoxy resin is more 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" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", " "HP-7200H", "HP-7200HHH" (dicyclopentadiene epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (dnaphthyl Ether epoxy resin), "EPPN-502H" (triphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", " "NC3000L", "NC3100" (biphenyl-type epoxy resin), "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" (naphthol novolac-type epoxy resin), Mitsubishi "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" made by chemical company ( Type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, "YL7800" (制 -type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid manufactured by Mitsubishi Chemical Corporation) Bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolac type epoxy resin), "YX4000HK" (Lianjia) manufactured by Mitsubishi Chemical Corporation Phenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, and "YL7800" (fluorene-type epoxy resin manufactured by Mitsubishi Chemical Corporation) ), "JER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These systems can be used alone or in combination of two or more.

The content of the solid epoxy resin in the resin composition is from the viewpoint of adjusting the viscosity of the resin composition. When the non-volatile content in the resin composition is set to 100% by mass, it is preferably 0.1% by mass or more. 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 obtained, but it is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.

The epoxy equivalent of the solid epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1000. By setting it as this range, the crosslinking density of hardened | cured material will be sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent of a solid epoxy resin can be measured in accordance with JIS K7236, and refers to the mass of a resin containing 1 equivalent of an epoxy group.

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

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

The 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 depending on the mass ratio. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, it can be obtained that i) it can have moderate adhesiveness when it is used in the form of a resin sheet, and ii) when it is used in the form of a resin sheet, it has Sufficient flexibility to improve handling properties, and iii) the effect of obtaining a hardened material having sufficient breaking strength and the like. From the viewpoint of the effects of i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin / liquid epoxy resin) is preferably 0.05 in terms of mass ratio. The range of ~ 0.8, more preferably the range of 0.1 ~ 0.5.

    <(c) Inorganic filler>    

The resin composition contains (c) an inorganic filler. The material of the inorganic filler is not particularly limited, but examples thereof include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and hydroaluminum Ores, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth acid, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like. Of these, silicon dioxide is particularly suitable. As the silicon dioxide, a spherical silicon dioxide is preferred. The inorganic filler may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, and more preferably 2.2 μm or less in terms of improving the circuit embedding property and obtaining an insulating layer having a low surface roughness. , And more preferably 2 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such average particle diameters include "YC100C", "YA050C", "YA050C-MJE", "YA010C", and "UFP-30" manufactured by Denka Kogyo, manufactured by Admatechs. , "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS-5N" made by Tokuyama, "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" made by Admatechs, "SO-C1" and so on.

The average particle diameter of the inorganic filler can be measured using a laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. It is preferable that the sample is measured by dispersing the inorganic filler in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd. can be used.

In order to improve the moisture resistance and dispersibility of the inorganic filler, an amine-based silane coupling agent, an epoxy silane-based coupling agent, a mercapto silane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, It is preferable to perform the treatment by using one or more surface treatment agents such as an organic silazane compound and a titanate-based coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Silane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-4803" (Long-chain epoxy-type silane coupling agent) and the like.

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

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, the inorganic filler was surface-treated using a solvent having a sufficient amount of MEK as a surface treatment agent, and then ultrasonically washed at 25 ° C for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler was measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler in the resin composition is from 50% to 95% by mass from the viewpoint that an insulating layer having a lower specific permittivity and a lower thermal expansion rate can be obtained. It is preferably 55 mass% or more, more preferably 60 mass% or more, and even more preferably 65 mass% or more. From the viewpoint of the mechanical strength of the insulating layer (specifically, the degree of stretch), the upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

    <(d) Hardener>    

The resin composition may contain (d) a hardener. The hardener is not particularly limited as long as it has a function of hardening the resin such as the component (b), and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and benzo. Based hardeners, cyanate ester based hardeners, and carbodiimide based hardeners. A hardening agent can be used individually by 1 type or in combination of 2 or more types. (d) The component is preferably one or more selected from a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a cyanate-based hardener, and is selected from a phenol-based hardener and an active ester. One or more types of the hardener are more preferable.

As the phenol-based hardener and naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. From the viewpoint of adhesion with the wiring layer, a nitrogen-containing phenol-based hardener is more preferable, and a triazine skeleton-containing phenol-based hardener is more preferable. Among these, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint that heat resistance, water resistance, and adhesion to the wiring layer can be highly satisfied.

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

From the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer, an active ester-based hardener is also preferred. The active ester-based hardener is not particularly limited. Generally, it has high reactivity by using two or more phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds in one molecule. Ester-based compounds are preferred. The active ester-based hardener is preferably prepared by subjecting a carboxylic acid compound and / or a thiocarboxylic acid compound to a condensation reaction with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is hardened. The agent is also preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromelic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, pyrogallol, dicyclopentadiene type diphenol compound, phenol Novolac, etc. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetic acid compound of phenol novolac, and benzoic acid compounds containing a phenol novolac compound. Active ester compounds are preferred, and among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit formed by a naphthyl-bicyclopentyl-naphthyl group.

Among commercially available active ester hardeners, examples of active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", " "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); as the active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Corporation); and ethyl alcohol containing phenol novolac Examples of the active ester compound of the halogenated compound include "DC808" (manufactured by Mitsubishi Chemical Corporation). Examples of the active ester compound of the benzated halogenated compound containing phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation); Examples of the active ester-based hardener of the acetic acid compound of novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation). Examples of the active ester-based hardener of the phenolic compound of phenol novolac include "YLH1026" (Mitsubishi Chemical company), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

As benzo Specific examples of the system hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-naphthylcyanate), 4,4 ' -Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether And other bifunctional cyanate resins, polyphenols derived from phenol novolac and cresol novolac, and prepolymers obtained by partially triazinating these cyanate resins. Specific examples of the cyanate-based hardener include "PT30" and "PT60" (both are phenol novolac-type polyfunctional cyanate resins), "BA230", and "BA230S75" (double Some or all of the phenol A dicyanate is triazinated to form a trimer prepolymer).

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

When the resin composition contains the component (d), the content of the hardener in the resin composition is not particularly limited, but when the nonvolatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or less. 8 mass% or less is preferable, and 5 mass% or less is more preferable. The lower limit is not particularly limited, but is preferably 1% by mass or more.

    <(e) Hardening accelerator>    

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

Examples of the phosphorous-based hardening accelerator include triphenylphosphine, a phosphonium borate compound, a phenylphosphonium tetraphenylborate, an n-butylphosphonium tetraphenylborate, and a tetrabutylphosphonium decanoate. Salt, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine, tetrabutylphosphonium Decanoate is preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-, (Dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., with 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4,0) -undecene is preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole salt trimellitate, 1-cyanoethyl-2benzene Imidazole salt trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-undecylimidazole- (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 trimerization Cyanide adduct, 2-phenylimidazole trimer isocyanide adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a] benzimidazole, 1- Dialkyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like, and the adducts of imidazole compounds and epoxy resins, with 2- Ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

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

Examples of the guanidine-based hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, and diamine. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl- 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide , 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, etc. Dicyanodiamine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetoacetone and cobalt (III), and copper complexes such as copper (II) acetoacetone. , Organic zinc complexes such as acetamidine zinc (II), organic iron complexes such as iron (III) acetone, organic nickel complexes such as nickel (II) acetone, and manganese acetone acetone (II) and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains the (e) component, the content of the hardening accelerator in the resin composition is not particularly limited, but when the total amount of the non-volatile components of the (b) component and (d) the hardener is set to 100% by mass, It is preferably 0.01% by mass to 3% by mass.

    <(f) Flame retardant>    

The resin composition may contain (f) a flame retardant. Examples of the flame retardant include organic phosphorus-based flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, polysiloxane flame retardants, and metal hydroxides. A flame retardant can be used individually by 1 type or in combination of 2 or more types.

As the flame retardant, a commercially available product can be used, and examples thereof include "HCA-HQ" manufactured by Sanko, and "PX-200" manufactured by Daiba Chemical Industries.

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

    <(g) any additives>    

Depending on the required resin composition, other additives may be further included. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; and binders, thickeners, and consumer additives. Resin additives such as foaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

    <Physical properties of resin composition>    

The resin composition of the present invention is thermally hardened at 180 ° C. for 1 hour, and the elasticity of the obtained hardened product at 23 ° C. is 18 GPa or less, preferably 15 GPa or less, and more preferably 13 GPa or less, 11 GPa or less, or 10 GPa or less. The lower limit is not particularly limited, but may be set to, for example, 0.01 GPa or more, 0.5 GPa or more, 1 GPa or more. By setting the elastic modulus to 18 GPa or less, it is possible to suppress the occurrence of warpage of the cured product. The above-mentioned elastic modulus can be measured by a method described in "Measurement of Elasticity" described later.

The resin composition of the present invention is thermally hardened at 180 ° C. for 1 hour, and the specific permittivity of the obtained hardened product at 23 ° C. and a measurement frequency of 5.8 GHz is 3.5 or less, preferably 3.4 or less, and more preferably 3.3 or less. The lower limit is not particularly limited, but may be set to, for example, 1 or more, 1.1 or more, 1.2 or more. By setting it within the above range, the CTE will be reduced and the amount of warpage can be suppressed. The specific permittivity can be measured by the method described in "Measurement of specific permittivity and dielectric tangent" described later.

The resin composition of the present invention is thermally hardened at 180 ° C for 1 hour. The specific permittivity of the obtained hardened product at 23 ° C and a measurement frequency of 1GHz is preferably 3.6 or less, preferably 3.5 or less, and more preferably 3.4 or less. good. The lower limit is not particularly limited, but may be set to, for example, 1 or more, 1.1 or more, 1.2 or more. By setting it within the above range, the CTE will be reduced and the amount of warpage can be suppressed. The specific permittivity can be measured by the method described in "Measurement of specific permittivity and dielectric tangent" described later.

In addition, the resin composition of the present invention was thermally cured at 180 ° C for 1 hour, and the specific permittivity of the obtained cured product at 23 ° C and a measurement frequency of 5.8GHz was compared with the specific permittivity of the cured product at 23 ° C and a measurement frequency of 1GHz. The difference is 0.3 or less, preferably 0.25 or less, and more preferably 0.23 or less, more preferably 0.2 or less, and still more preferably 0.15 or less, 0.1 or less, 0.05 or less, 0.005 or less, or 0.002 or less. The lower limit is not particularly limited, but may be set to, for example, 0 or more, 0.001 or more. By setting it within the above range, the insulation reliability is excellent and warpage is suppressed, so that an insulation layer with low CTE can be obtained. The above-mentioned difference in specific permittivity can be measured by a method described in "Measurement of specific permittivity and dielectric tangent" described later.

The resin composition of the present invention is thermally hardened at 180 ° C. for 1 hour. The dielectric tangent of the obtained hardened product at 23 ° C. and a measurement frequency of 5.8 GHz is preferably 0.01 or less, more preferably 0.009 or less, and more preferably 0.008 or less. The lower limit is not particularly limited, but may be set to, for example, 0 or more, 0.0001 or more. By setting it in the said range, the insulation layer which can suppress insertion loss (Insertion Loss) can be obtained. The above-mentioned dielectric tangent can be measured according to the method described in "Measurement of Specific Dielectric Ratio and Dielectric Tangent" described later.

The resin composition of the present invention is thermally hardened at 180 ° C. for 1 hour. The dielectric tangent of the obtained hardened product at 23 ° C. and a measurement frequency of 1 GHz is preferably 0.01 or less, more preferably 0.009 or less, and more preferably 0.008 or less. The lower limit is not particularly limited, but may be set to, for example, 0 or more, 0.0001 or more. By setting it in the said range, the insulating layer which can suppress insertion loss can be obtained. The above-mentioned dielectric tangent can be measured according to the method described in "Measurement of Specific Dielectric Ratio and Dielectric Tangent" described later.

The resin composition of the present invention is thermally hardened at 180 ° C for 1 hour. The difference between the dielectric tangent of the hardened product at 23 ° C and a measurement frequency of 5.8GHz is better than the dielectric tangent of the hardened product at 23 ° C and a measurement frequency of 1GHz. It is 0.002 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 set to, for example, 0 or more. By setting it in the said range, the insulating layer which can suppress insertion loss can be obtained. The above-mentioned difference in dielectric tangent can be measured according to the method described in "Measurement of Specific Dielectric Ratio and Dielectric Tangent" described later.

The resin composition of the present invention is thermally cured at 100 ° C. for 30 minutes, and further thermally cured at 180 ° C. for 30 minutes. The resulting cured product exhibits so-called properties capable of suppressing the occurrence of warpage. The size of the warpage is preferably less than 2 cm, more preferably 1.5 cm or less, and still more preferably 1 cm or less. The measurement of warpage can be measured by the method described in "Evaluation of Warpage" described later.

The resin composition of the present invention was thermally hardened at 180 ° C for 1 hour, and the obtained hardened product showed a so-called 200-hour damp insulation resistance value (humidity) under the conditions of 130 ° C, 85% relative humidity, and 3.3V DC applied voltage. Insulation reliability) is a good result. The above resistance value is preferably 10 ⁸ Ω or more, more preferably 10 ⁹ Ω or more, and even more preferably 10 ¹⁰ Ω or more. The measurement of the reliability of wet insulation can be measured according to the method described in "Evaluation of the reliability of wet insulation" described later.

The resin composition of the present invention is thermally cured at 180 ° C for 1 hour, and the linear thermal expansion coefficient (CTE) of the obtained cured product is preferably 20 ppm / ° C or lower, and more preferably 15 ppm / ℃ or lower, more preferably 10 ppm / ℃ or lower. The lower limit is not particularly limited, but may be set to 1 ppm / ° C or higher. The linear thermal expansion coefficient can be measured in the order of <Measurement of linear thermal expansion coefficient (CTE)> described later.

The resin composition of the present invention can obtain an insulating layer having excellent insulation reliability, which can suppress the occurrence of warping, and has a low coefficient of linear thermal expansion. In addition, since the components (b1) and (b2) are included, the compatibility of the component (a) is good . Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a semiconductor wafer package (resin composition for an insulating layer of a semiconductor wafer package), A resin composition of an insulating layer (resin composition for an insulating layer of a circuit board); further, a resin composition for forming an interlayer insulating layer on top of which a conductor layer is formed by plating (which is formed by plating) can be suitably used. Resin composition for an interlayer insulating layer of a circuit board forming a conductor layer).

In addition, a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer) and a resin composition for forming wiring on a semiconductor wafer (resin composition for forming a semiconductor wafer wiring) can be suitably used.

    [Resin sheet]    

The resin sheet of the present invention includes a support and a resin composition layer bonded to the support, and the resin composition layer is formed of the resin composition of the present invention.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, and 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 can usually be set to 1 μm or more, 5 μm or more, 10 μm or more, and the like.

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

When a thin film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PET") Polyesters, polycarbonates (hereinafter referred to as "PC"), polyacrylic methyl methacrylate (PMMA), etc. Acetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The support may be subjected to a matting treatment or a corona discharge treatment to the surface bonded to the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can be used. The mold release agent used as the mold release layer of the support provided with a mold release layer may be selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. One or more release agents. A commercially available product can be used as the support with a release layer, for example, a PET film having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "SK-1" manufactured by Lintec Corporation. , "AL-5", "AL-7", "Lumirror T60" made by Toray, "PUREX" made by Teijin, "Unipeel" made by Unitika, and so on.

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 provided with a release layer is used, the entire thickness of the support provided with a release layer is preferably within the above range.

The resin sheet can be produced, for example, by preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a die coater, and drying the resin varnish. A resin composition layer is formed.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, acetic acid cellosolve, propylene glycol monomethyl ether acetate, and carbidine Acetic esters such as alcohol acetate, cellulosics and carbitol such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide (DMAc) and ammonium-based solvents such as N-methylpyrrolidone and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In the resin sheet, on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support), a protective film may be further laminated to the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent adhesion of foreign matter or the like to the surface of the resin composition layer or to form a flaw. The resin sheet can be rolled into a roll and stored. When the resin sheet has a protective film, it can be used by peeling the protective film.

It is also possible to use a prepreg, which is formed by replacing a resin sheet of the present invention with a sheet-like fiber substrate and impregnating the resin composition of the present invention with the sheet-like fiber substrate.

The sheet-like fibrous substrate used for the prepreg is not particularly limited, and glass cloth, aromatic aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like that are generally used as a substrate for a prepreg can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber substrate is preferably 900 μm or less, more preferably 800 μm or less, more preferably 700 μm or less, and still more preferably 600 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, but can usually be set to 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

A prepreg can be manufactured by a well-known method, such as a hot-melt method and a solvent method.

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

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

The resin sheet of the present invention can be suitably used for sealing a semiconductor wafer (resin sheet for sealing a semiconductor wafer) or forming a wiring on a semiconductor wafer (resin sheet for forming a semiconductor wafer wiring). -Out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, etc. Moreover, it can also be used suitably for MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor wafer to a board | substrate.

The resin sheet of the present invention is also suitable for use in other broad applications requiring high insulation reliability, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

    [Circuit Board]    

The circuit board of the present invention is an insulating layer including a cured product of the resin composition of the present invention.

The manufacturing method of the circuit substrate of the present invention, as shown in an example shown in FIGS. 1 and 2, includes the following steps: (1) a step of preparing a substrate with a wiring layer, the substrate with the wiring layer having A base material and a wiring layer provided on at least one side of the base material; (2) laminating the resin sheet of the present invention to a base material with a wiring layer in a manner that the wiring layer is an embedded resin composition layer, And a step of thermally curing the insulating layer to form an insulating layer; (3) a step of connecting the wiring layers to each other.

Moreover, the manufacturing method of a circuit board may include (4) the process of removing a base material.

As long as the wiring layer can be connected between layers, step (3) is not particularly limited, but at least any one of the following steps is preferred: a step of forming a through hole in the insulating layer and a conductor layer; and, insulating the The step of grinding or grinding the layer to expose the wiring layer.

    <Step (1)>    

Step (1) is a step of preparing a substrate with a wiring layer. The substrate with a wiring layer includes a substrate and a wiring layer provided on at least one side of the substrate. As shown in an example shown in FIG. 1 (A) and FIG. 2 (A), the substrate 10 with a wiring layer is a first metal layer 12, a first metal layer 12 The second metal layer 13 has a wiring layer 14 on a surface of the second metal layer 13 that is opposite to the surface of the substrate 11 side. Specifically, a dry film (photosensitive resist film) is laminated on a substrate, and a photomask is used to expose and develop under specified conditions to form a patterned dry film. Using the developed patterned dry film as a plating mask, a wiring layer was formed by an electroplating method, and then the patterned dry film was peeled. 1 and 2 have the first metal layer 12 and the second metal layer 13, but they may not have the first metal layer 12 and the second metal layer 13.

Examples of the substrate include glass epoxy substrates, metal substrates (stainless steel or cold rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate, a metal layer such as a copper foil may be formed on the surface of the substrate. As shown in FIGS. 1 (A) and 2 (A), a peelable first metal layer 12 and a second metal layer 13 (for example, copper with a carrier made by Mitsui Metals Co., Ltd.) can be formed on the surface of the substrate. Metal foils such as ultra-thin copper foil, trade name "Micro Thin").

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and dry films such as novolac resin and acrylic resin can be used. Commercially available dry film can also be used.

The conditions for laminating the substrate and the dry film are the same as those for laminating the resin sheet into the wiring layer in step (2) described later, and the same conditions apply to the preferred ranges.

After the dry film is laminated on the substrate, in order to form a desired pattern for the dry film, exposure and development are performed under a specified condition using a photomask.

The line width (circuit width) / pitch (width between circuits) ratio of the wiring layer is not particularly limited, but it is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), and more preferably 10/10 μm or less, and more preferably It is 5/5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or less. The pitch need not be the same for the entire wiring layer. The minimum pitch of the wiring layer can be 40 μm or less, 36 μm or less, or 30 μm or less.

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

The conductive material used for the wiring layer is not particularly limited. In a suitable 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. metal. The wiring layer may be a single metal layer or an alloy layer. Examples of the alloy layer include an alloy of two or more metals selected from the above-mentioned groups (for example, nickel‧chromium alloy, copper‧nickel alloy, and Copper ‧ titanium alloy). Among these, from the viewpoints of versatility, cost, and ease of patterning of the wiring layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred, or Alloy layers of nickel ‧ chromium alloy, copper ‧ nickel alloy, copper ‧ titanium alloy, and preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel chrome alloy An alloy layer, more preferably a single metal layer of copper.

It varies according to the desired design of the wiring board, but the thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, more preferably 10 to 20 μm, or 15 μm. In the step (3), if the step of grinding or grinding the insulating layer to expose the wiring layer and perform the interlayer connection of the wiring layer, the thickness of the wiring for the interlayer connection and the unconnected wiring are preferably different. The thickness of the wiring layer can be adjusted by repeating the aforementioned pattern formation. It varies according to the desired design of the wiring board, but the thickness of the thickest wiring layer (conductive pillar) in each wiring layer is preferably 100 μm or less and 2 μm or more. In addition, the wiring for interlayer connection may be a convex type.

After the wiring layer is formed, the dry film is peeled. The dry film can be peeled off using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns can be removed by etching or the like to form a desired wiring pattern. The distance between the formed wiring layers is the same as described above.

    <Step (2)>    

Step (2) is a step of laminating the resin sheet of the present invention on a substrate with a wiring layer and using a wiring layer as an embedded resin composition layer to form an insulating layer by thermal curing. As an example shown in FIG. 1 (B), the wiring layer 14 with the substrate with the wiring layer obtained in the aforementioned step (1) is laminated so as to be embedded in the resin composition layer 21 of the resin sheet 20 The resin composition layer 21 of the resin sheet 20 is thermally hardened to form an insulating layer (symbol 21 'in FIG. 1 (C) or FIG. 2 (B)). The resin sheet 20 is formed by laminating a resin composition layer 21 and a support 22 in this order.

The wiring layer and the resin sheet are laminated, and after removing the protective film of the resin sheet, for example, the resin sheet can be heated and pressed to the wiring layer from the support side. As a member which heat-presses a resin sheet to a wiring layer (henceforth a "heat-pressing member"), a heated metal plate (SUS mirror plate etc.), a metal roller (SUS roller), etc. are mentioned, for example. It is preferable that the heat-pressing member is not directly bonded to the resin sheet, but is pressed through an elastic material such as a heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the wiring layer.

Lamination of the wiring layer and the resin sheet may be performed by vacuum lamination after removing the protective film of the resin sheet. In the vacuum layer method, the heating and pressing temperature is preferably in the range of 60 ° C to 160 ° C, and more preferably in the range of 80 ° C to 140 ° C. The heating and pressing pressure is preferably 0.098MPa to 1.77MPa, and more preferably 0.29MPa to In the range of 1.47 MPa, the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of a pressure of 13 hPa or less.

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

After the resin composition layer is laminated on the substrate with the wiring layer embedded in the wiring layer, the resin composition layer is thermally cured to form an insulating layer. For example, the thermal curing conditions of the resin composition layer may vary depending on the type of the resin composition, but the curing temperature may be set in a range of 120 ° C to 240 ° C, and the curing time may be set in a range of 5 minutes to 120 minutes. Before the resin composition layer is thermally hardened, the resin composition layer may be preheated at a temperature lower than the curing temperature.

The support of a resin sheet can be peeled off after laminating the resin sheet on a substrate with a wiring layer and thermally curing it. As an example shown in FIG. 2 (B), the support can also be mounted on a resin. The sheet is peeled off before being laminated to the substrate with the wiring layer attached. Moreover, you may peel a support body before the roughening process process mentioned later.

    <Step (3)>    

Step (3) is a step of connecting the wiring layers between layers. In detail, a step of forming a through hole in the insulating layer, forming a conductor layer, and performing interconnection between the wiring layers (see FIGS. 1 (C) and (D)). Or, the step of grinding or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers (refer to FIG. 2 (C)).

If the steps of forming a through hole in an insulating layer, forming a conductor layer, and performing interlayer connection of a wiring layer are used, the formation of a via hole is not particularly limited. Examples include laser irradiation, etching, and mechanical drilling. Preferably, it is performed by laser irradiation. This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide laser, a YAG laser, an excimer laser, or the like as a light source. As shown in detail in FIG. 1 (C), in step (3), laser irradiation is performed from the surface side of the support 22, penetrates the support 22, the insulating layer 21 ', and exposes the wiring layer 14 to form a conductive layer.孔 31。 Hole 31.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out in any appropriate step by a conventional method in accordance with a selected method.

The shape of the through hole (that is, the shape of the opening contour when viewed in the extension direction) is not particularly limited, but is generally circular (slightly circular).

After the through-hole is formed, a stain removal step in the through-hole may be performed, a so-called de-smudge step. If the formation of a conductive layer described later is performed by a plating step, for example, a wet decontamination treatment may be performed on the through-holes. If the formation of a conductive layer is performed by a sputtering step, for example, electrical conductivity may be performed. A dry decontamination step such as a pulp treatment step. In addition, the stain removal step may be combined with a roughening treatment step.

Before forming the conductor layer, the through holes and the insulating layer may be roughened. The roughening treatment can be performed in a well-known order and conditions. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralizing liquid. The method of neutralization processing sequence.

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

Specifically, a plating seed layer 41 is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern in which a part of the plating seed layer is exposed is formed in accordance with a desired wiring pattern. An electrolytic plating layer 42 is formed on the exposed plating seed layer by electrolytic plating. At this time, while the electrolytic plating layer 42 is formed, the through-hole 31 may be buried by electrolytic plating to form the filled hole 61. After the electrolytic plating layer 42 is formed, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductive 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 dry film.

In addition to the linear wiring, the conductive layer may include electrode pads (pads) and the like that can mount external terminals. The conductive layer may be composed of only an electrode pad.

In addition, the conductive layer can be formed by forming a plating seed layer, then forming an electrolytic plating layer and filling holes without using a mask pattern, and then patterning by etching.

When the steps of grinding or grinding the insulating layer to expose the wiring layer and connecting the wiring layers are used, as the method of grinding or grinding the insulating layer, as long as the wiring layer can be exposed and the grinding or grinding surface is horizontal, It is not particularly limited, and a conventionally known grinding method or grinding method can be applied, and examples thereof include a chemical mechanical grinding method using a chemical mechanical grinding device, a mechanical grinding method such as buff, and a plane grinding method by rotating a grindstone. Wait. Similar to the steps of forming a through hole in an insulating layer, forming a conductor layer, and performing interconnection between wiring layers, a stain removal step, a roughening step may be performed, and a conductor layer may also be formed. In addition, as shown in an example shown in FIG. 2 (C), it is not necessary to expose the entire wiring layer 14 and a part of the wiring layer 14 may be exposed.

    <Step (4)>    

The method for manufacturing a circuit board may include a step (4) other than the steps (1) to (3). Step (4) is a step of removing the substrate and forming the circuit board 1 of the present invention, as an example shown in Figs. 1 (E) and 2 (D). The method of removing the substrate is not particularly limited. In a suitable embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous copper chloride solution. If necessary, the conductor layer can be peeled off from the substrate in a state protected by a protective film.

    [Semiconductor chip package]    

The first aspect of the semiconductor wafer package of the present invention is a semiconductor wafer package obtained by mounting a semiconductor wafer on the circuit board of the present invention. By bonding a semiconductor wafer to the circuit substrate of the present invention described above, a semiconductor wafer package can be manufactured.

As long as the terminal electrodes of the semiconductor wafer and the circuit wiring of the circuit board are conductively connected, the joining conditions are not particularly limited, and well-known conditions used in a flip-chip package of a semiconductor wafer can be used. In addition, the semiconductor wafer and the circuit board may be bonded through an insulating adhesive.

In a suitable embodiment, a semiconductor wafer is pressed against a circuit board. The pressing conditions can be set, for example, in a range of a pressing temperature of 120 ° C to 240 ° C (preferably in a range of 130 ° C to 200 ° C, and more preferably in a range of 140 ° C to 180 ° C) and a pressing time of 1 second. Clock to 60 seconds (preferably 5 seconds to 30 seconds).

In another suitable embodiment, the semiconductor wafer is reflow-bonded to the circuit board. The reflow conditions can be set in a range of, for example, 120 ° C to 300 ° C.

After the semiconductor wafer is bonded to the circuit substrate, for example, the semiconductor wafer is filled with a mold underfill, thereby obtaining a semiconductor wafer package. The method of filling with a mold underfill material is implemented using a well-known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill.

The second aspect of the semiconductor wafer package of the present invention, for example, an exemplary semiconductor wafer package (Fan-out WLP) 100 shown in FIG. 3, is made by using the resin composition or resin sheet of the present invention to manufacture the sealing layer 120. Into a semiconductor wafer package. The semiconductor wafer package 100 is provided with a semiconductor wafer 110, a sealing layer 120 (formed by covering the periphery of the semiconductor wafer 110), and a rewiring formation layer (insulating layer) 130 (covered by the sealing layer with the semiconductor wafer 110). The covered side is the opposite side), the conductor layer (rewiring layer) 140, the solder resist layer 150, and the bump 160. The manufacturing method of such a semiconductor chip package includes the following steps: (A) a step of laminating a temporarily fixed film to a substrate; (B) a step of temporarily fixing a semiconductor wafer on the temporarily fixed film; (C) a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor wafer, or coating the resin composition of the present invention on a semiconductor wafer and thermally hardening it to form a sealing layer; The step of peeling the substrate and the temporary fixing film from the semiconductor wafer; (E) the step of forming a rewiring formation layer (insulating layer) on the surface of the semiconductor wafer after the substrate and the temporary fixing film are peeled off; (F) the step of A step of forming a conductor layer (rewiring layer) on the wiring forming layer (insulating layer); and (G) a step of forming a solder resist layer on the conductor layer.

In addition, the method for manufacturing a semiconductor wafer package may include the following steps: (H) a step of cutting a plurality of semiconductor wafer packages into individual semiconductor wafer packages and singulating the individual semiconductor wafer packages.

    <Step (A)>    

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

The material used for the substrate is not particularly limited. Examples of the substrate include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); epoxy resin and the like are penetrated into glass fibers and heat-hardened. Substrates (eg, FR-4 substrates); substrates made of bismaleimide imine triazine resin (BT resin), and the like.

The temporary fixing film is not particularly limited as long as the film can be temporarily fixed while being peeled from the semiconductor wafer in step (D) described later. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include REVALPHA manufactured by Nitto Denko Corporation.

    <Step (B)>    

Step (B) is a step of temporarily fixing the semiconductor wafer on the temporarily fixing film. The temporary fixing of the semiconductor wafer can be performed using a known device such as a flip chip bonding machine and a die bonding machine. The arrangement layout and number of semiconductor wafers can be appropriately set according to the shape and size of the temporarily fixed film, the production quantity of the intended semiconductor package, and the like. For example, it can be arranged in a matrix of a plurality of rows and a plurality of columns. Temporarily fixed.

    <Step (C)>    

Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor wafer, or coating the resin composition of the present invention on a semiconductor wafer and thermally curing it to form a sealing layer. In step (C), the resin composition layer of the resin sheet of the present invention is preferably laminated on a semiconductor wafer and thermally cured to form a sealing layer.

The lamination of the semiconductor wafer and the resin sheet can be performed by, for example, heating and pressing the resin sheet onto the semiconductor wafer from the support side after removing the protective film of the resin sheet. As a member which heat-presses a resin sheet to a semiconductor wafer (henceforth a "heat-pressing member"), the heated metal plate (SUS mirror plate etc.), a metal roller (SUS roller), etc. are mentioned, for example. It is preferable that the heat-pressing member is not directly bonded to the resin sheet, but is pressed through an elastic material such as a heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the semiconductor wafer.

In addition, the lamination of the semiconductor wafer and the resin sheet may be performed by vacuum lamination after removing the protective film of the resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) in the method for manufacturing a circuit board, and the preferred ranges are also the same.

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

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

    <Step (D)>    

Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor wafer. The method of peeling can be appropriately changed according to 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 substrate side to temporarily fix the film. How to reduce the adhesion of the film and peel it off.

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

    <Step (E)>    

Step (E) is a step of forming a rewiring forming layer (insulating layer) on the surface of the semiconductor wafer after the substrate and the temporary fixing film are peeled off.

The material for forming the redistribution forming layer (insulating layer) is not particularly limited as long as it is insulating when the redistribution forming layer (insulating layer) is formed. From the standpoint of ease of manufacturing a semiconductor chip package, Preferred are photosensitive resins and thermosetting resins. As the thermosetting resin, a resin composition having the same composition as the resin composition used to form the resin sheet of the present invention can be used.

After the redistribution forming layer (insulating layer) is formed, through-holes may be formed in the redistribution forming layer (insulating layer) for interlayer connection between the semiconductor wafer and a conductor layer described later.

When forming a through-hole, when the material for forming the redistribution wiring layer (insulating layer) is a photosensitive resin, first, irradiate the surface of the redistribution wiring layer (insulating layer) with an active energy ray through a mask pattern To harden the outermost wiring layer of the irradiated portion.

Examples of the active energy rays include ultraviolet rays, visible rays, electron rays, and X-rays. Ultraviolet rays are particularly preferred. The amount of ultraviolet radiation and the irradiation time can be appropriately changed according to the photosensitive resin. As an exposure method, any of the following exposure methods can be used: a contact exposure method in which a mask pattern is adhered to a rewiring formation layer (insulating layer) and exposed, and a mask pattern is not adhered to a rewiring. A non-contact exposure method in which a layer (insulating layer) is formed and exposure is performed using parallel light.

Next, a redistribution layer (insulating layer) is developed and unexposed parts are removed, thereby forming a through hole. The development system is suitable for wet development or dry development. As the developer used for the wet development, a known developer can be used.

Examples of the development method include a dipping method, a mixing method, a spray method, a brush application method, and a doctor blade method. The mixing method is suitable in terms of resolution.

When the material for forming the rewiring formation layer (insulating layer) is a thermosetting resin, the formation of the through hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. may be mentioned, and laser irradiation is preferred. Come on. Laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide laser, a UV-YAG laser, an excimer laser, or the like as a light source.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out in any appropriate step by a conventional method in accordance with a selected method.

The shape of the through hole (that is, the shape of the opening contour when viewed in the extension direction) is not particularly limited, but is generally circular (slightly circular). The diameter of the top port of the through hole (the opening diameter on the surface of the rewiring formation layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even 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 more preferably 20 μm or more.

    <Step (F)>    

Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method for forming a conductor layer on a rewiring formation layer (insulating layer) is the same as the method for forming a conductor layer after forming a through hole in an insulating layer in the step (3) of the method for manufacturing a circuit board, and the preferred range is The same. Alternatively, steps (E) and (F) may be repeated to alternately stack (build-up) the conductor layer (rewiring layer) and the redistribution forming layer (insulating layer).

    <Step (G)>    

Step (G) is a step of forming a solder resist layer on the conductor layer.

The material for forming the solder resist layer is not particularly limited as long as it has insulation properties when the solder resist layer is formed. From the standpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and thermosetting properties are preferred. Resin. As the thermosetting resin, a resin composition having the same composition as the resin composition used to form the resin sheet of the present invention can be used.

In step (G), bumping for forming bumps may be performed as needed. The bump processing can be performed using a known method such as solder balls or solder plating. The formation of through holes in bump processing can be performed in the same manner as in step (E).

    <Step (H)>    

In addition to steps (A) to (G), a method for manufacturing a semiconductor chip package may include step (H). Step (H) is a step of cutting a plurality of semiconductor wafer packages into individual semiconductor wafer packages, and singulating the individual semiconductor wafer packages.

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

The third aspect of the semiconductor wafer package of the present invention is to use the resin composition or resin sheet of the present invention to manufacture a rewiring formation layer in an example semiconductor wafer package (Fan-out type WLP) shown in FIG. 3 (Insulation layer) 130 and a semiconductor chip package made of a solder resist layer 150.

    [Semiconductor device]    

Examples of the semiconductor device capable of encapsulating the semiconductor chip package of the present invention include electrical appliances (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions). And various semiconductor devices such as motorcycles, automobiles, trams, ships, and airplanes.

    [Example]    

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. However, in the following descriptions, "parts" and "%" indicating quantities, unless otherwise specified, represent "mass parts" and "mass%", respectively.

    (Production of hardened materials for evaluation)    

On the untreated surface of the mold release agent-treated PET film ("501010" manufactured by Lintec, thickness of 38 μm, 240 mm square), a glass cloth substrate and an epoxy resin-coated copper-clad laminate were laminated on both sides (manufactured by Matsushita Electric Works). "R5715ES", thickness 0.7mm, 255mm square), and four sides were fixed with polyimide adhesive tape (width 10mm) (hereinafter referred to as "fixed PET film").

The resin varnishes produced in the examples and comparative examples were coated with an alkyd resin-based release agent ("AL-5 manufactured by Lintec Corporation") using a die coater so that the thickness of the dried resin composition layer became 40 µm. ") A PET film (" Lumirror R80 "manufactured by Toray Co., Ltd., having a thickness of 38 µm and a softening point of 130 ° C, hereinafter referred to as" release PET ") was dried at 80 ° C to 120 ° C (average 100 ° C). 10 minutes to obtain a resin sheet. Using a batch-type vacuum pressure laminating machine (Nikko-materials, 2-stage build-up laminating machine, CVP700), the resin composition layer and the release agent treatment surface of the fixed PET film were connected to each other so that each resin A sheet (thickness: 40 μm, 200 mm square) was laminated in the center to obtain a resin sheet. The lamination treatment was performed by decompressing for 30 seconds and setting the air pressure to 13 hPa or less, and then pressing at 100 ° C and a pressure of 0.74 MPa for 30 seconds.

Next, it was put into a 100 ° C. baking oven under a temperature condition of 100 ° C. for 30 minutes, and then moved to a 175 ° C. baking oven under a temperature condition of 175 ° C. for 30 minutes to heat-harden it. After that, the substrate was taken out to room temperature, and the release PET was peeled off from the resin sheet with a support, and then it was thermally hardened under a curing condition of 90 minutes after being put into a baking oven at 190 ° C.

After heat curing, the polyimide and adhesive tape were peeled off, and the cured product was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate, and the PET film ("501010" by Lintec) was also peeled off. Thereby, a flaky hardened | cured material was obtained. The obtained hardened | cured material is called "the hardened | cured material for evaluation."

    <Measurement of linear thermal expansion coefficient (CTE)>    

The hardened material for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm. The thermo-mechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) was used to perform thermo-mechanical analysis by a tensile load method. Specifically, the test piece was installed in the thermo-mechanical analysis device, and the measurement was performed twice under continuous measurement conditions under a load of 1 g and a temperature increase rate of 5 ° C./minute. Then, from the two measurements, the linear thermal expansion coefficient (ppm / ° C) in the plane direction in the range from 25 ° C to 150 ° C was calculated.

    <Measurement of elasticity>    

The hardened material for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. This test piece was measured for tensile strength using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ° C was determined. The measurement is performed in accordance with JIS K7127.

    <Measurement of specific permittivity and dielectric tangent>    

The resin varnishes obtained in the examples and comparative examples were uniformly applied to a PET film (Lintec Corporation, "PET501010") subjected to mold release treatment so that the thickness of the dried resin composition layer became 40 µm by a die coater. ) And dried at 80 to 110 ° C (average 95 ° C) for 6 minutes. Then, it heat-processed at 180 degreeC for 1 hour, and peeled from the PET film, and obtained the hardened | cured material film. This cured film was cut into a length of 80 mm and a width of 2 mm, and was used as an evaluation sample. For this evaluation sample, an HP8362B device manufactured by Agilent Technologies was used to measure the specific permittivity at a temperature of 23 ° C., a measurement frequency of 1 GHz or 5.8 GHz, and a dielectric tangent by a cavity resonator perturbation method. The measurement was performed on two test pieces, and an average value was calculated. Further, the difference between the specific permittivity (average value) at the measurement frequency of 1 GHz and the specific permittivity (average value) at the measurement frequency of 5.8 GHz was obtained, and the dielectric tangent (average value) at the measurement frequency of 1 GHz was calculated. Difference in dielectric tangent (average) at a frequency of 5.8 GHz.

    <Assessment of Moisture Reliability>         (Modulation of evaluation substrate)         (1) Substrate treatment of inner circuit board    

As the inner-layer circuit board, a glass cloth substrate epoxy resin-coated copper-clad laminate (copper foil) having circuit conductors (copper) formed on both sides with a wiring pattern (residual copper rate of 70%) through a 1 mm square grid was prepared. Thickness is 18 μm, the thickness of the substrate is 0.3 mm, and “R1515F” manufactured by Panasonic Corporation). Both sides of this inner-layer circuit board were immersed in "CZ8100" manufactured by MEC Corporation, and a copper surface was roughened (a copper etching amount of 0.7 μm).

    (2) Lamination of resin sheet    

Each resin varnish produced in the examples and comparative examples was coated on a release PET with a die coater so that the thickness of the dried resin composition layer became 35 μm, and was 80 ° C. to 120 ° C. (average 100 ° C.). ) For 10 minutes to obtain a resin sheet. A batch-type vacuum pressure laminating machine (Nikko-materials, 2-step build-up laminating machine, CVP700) was used to connect the resin composition layer to the inner circuit board, and the produced resin sheet layer Closed on both sides of the inner circuit board. The lamination system was carried out by reducing the pressure for 30 seconds, setting the air pressure to 13 hPa or less, and pressing at 120 ° C and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 60 seconds.

    (3) Thermal hardening of the resin composition layer    

The inner circuit board on which the resin sheet has been laminated is put into a 100 ° C baking oven at a temperature of 100 ° C for 30 minutes, and then moved to a 175 ° C baking oven at a temperature of 175 ° C. For 30 minutes, heat curing was performed to form an insulating layer.

    (4) Formation of through holes    

A CO ₂ laser processing machine "605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation was used to irradiate the laser from the top of the support from the top of the insulating layer and the support to form a top port diameter on the insulating layer of the grid-shaped conductor. (70 μm) through hole. The laser irradiation conditions were performed with 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 pulse intermittent mode (10 kHz).

    (5) Steps for roughening    

The release PET is peeled from the inner-layer circuit board provided with a through hole, and a stain removal process is performed. The stain removal treatment is performed by the wet stain removal treatment described below.

Wet type stain removal treatment: in a swelling liquid ("Swelling Dip SecuriganthP" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, and then in an oxidant solution ("Concentrate Compact CP" manufactured by Atotech Japan, 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 in a neutralizing solution ("Reduction" manufactured by Atotech Japan solution Securiganth P ", sulfuric acid aqueous solution) was immersed at 40 ° C for 5 minutes, and then dried at 80 ° C for 15 minutes.

    (6) Steps for forming a conductor layer         (6-1) Electroless plating process    

In order to form a conductor layer on the surface of the above-mentioned inner-layer circuit board, a plating step (copper plating step using a chemical solution manufactured by Atotech Japan Corporation) including the following steps 1 to 6 is performed to form a conductor layer.

    1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer provided with through holes)    

The surface of the inner-layer circuit board was cleaned at 60 ° C for 5 minutes using Cleaning Cleaner Securiganth 902 (trade name).

    2. Soft etching (cleaning in through holes)    

The surface of the inner-layer circuit board was treated with a sulfuric acid-sodium peroxodisulfate aqueous solution at 30 ° C for 1 minute.

    3.Pre-impregnation (for adjusting the charge on the surface of the insulating layer of Pd)    

The surface of the inner-layer circuit board was treated with Pre.Dip Neoganth B (trade name) at room temperature for 1 minute.

    4. Activator Contribution (Pd Contribution to the Surface of the Insulating Layer)    

The surface of the inner-layer circuit board was treated with Activator Neoganth 834 (trade name) at 35 ° C for 5 minutes.

    5. Reduction (reduction of Pd imparted to the insulating layer)    

The surface of the inner layer circuit board was treated at 30 ° C for 5 minutes using a mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (Trade name).

    6. Electroless copper plating step (Cu is deposited on the surface of the insulating layer (Pd surface))    

On the surface of the inner circuit board, a mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) was used. And treated at 35 ° C 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 copper was filled in the through holes using a chemical solution manufactured by Atotech Japan. After that, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm that is communicated with the via hole, and a circular conductor with a diameter of 10 mm that is not connected to the lower layer conductor are used. In the pattern, a conductor layer having a pad and a conductor pattern is formed on the surface of the insulating layer with a thickness of 10 μm. Next, an annealing treatment was performed at 190 ° C for 90 minutes. This substrate was used as the evaluation substrate A.

    (Measurement of insulation layer thickness between conductor layers)    

The evaluation substrate A was subjected to cross-sectional observation using a FIB-SEM composite apparatus ("SMI3050SE" manufactured by SII Nanotechnology Corporation). Specifically, a cross section perpendicular to the surface of the conductor layer was cut out by FIB (Focused Ion Beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. A cross-sectional SEM image of five randomly selected locations was observed for each sample, and the average value was used as the thickness of the insulating layer between the conductor layers.

    (Assessment of Moisture Insulation Reliability of Insulation Layer)    

The 10 mm-diameter circular conductor side of the evaluation substrate A obtained above was used as a positive (+) electrode, and the grid-conductor (copper) side of the inner-layer circuit board connected to a pad having a diameter of 1 mm was used as a negative (-) electrode. , Using a highly accelerated life test device ("PC422-R8D" manufactured by Hirayama Seisakusho, Ltd.), under conditions of 130 ° C, 85% relative humidity, and 3.3V DC applied voltage, an electrochemical migration tester ("IMG8600B" manufactured by IMVCORPORATION Corporation) was used. ") Measure the insulation resistance value in 200 hours of humidity. This measurement was performed 6 times, and the moisture resistance value of all 6 test pieces was set to "○" when the moisture resistance value was 10 ⁸ Ω or more, and to "×" when only one was less than 10 ⁸ Ω.

    <Evaluation of warpage amount>    

A batch type vacuum pressure laminating machine (Nikko-materials Co., Ltd. two-stage build-up laminating machine "CVP700") was used to laminate the resin sheet used for preparing the evaluation substrate on both sides of the glass cloth substrate BT resin. After removing the PET film on one side of a copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.15 mm, Mitsubishi Gas Chemical Co., Ltd. “HL832NSF LCA”, size: 15 cm × 18 cm), remove the PET film at 100 ° C for 30 minutes, and then It was thermally hardened at 180 ° C for 30 minutes, and the amount of warpage placed on a plane was confirmed. The average value of the warpage amount of each of the four corners was set to "○" when the curvature was less than 1 cm, "△" to 1 to 2 cm, and "×" to be 2 cm or more.

    [Synthesis example 1]         <Manufacture of Elastomer A>    

In a reaction vessel, 69 g of a bifunctional hydroxyl-terminated polybutadiene (G-3000, manufactured by Soda Co., Ltd., number average molecular weight = 3000, hydroxyl equivalent weight = 1800 g / eq.) Was mixed with Ipuzoru 150 (aromatic hydrocarbon system) Solvent: 40 g by Idemitsu Petrochemical Co., Ltd. and 0.005 g of dibutyltin dilaurate were dissolved uniformly. When it became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added, and the reaction was performed for about 3 hours. Next, after cooling the reaction product to room temperature, 23 g of a cresol novolac resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent weight = 117 g / eq.) And diethylene glycol ether acetate were added thereto. 60 g (manufactured by DAICEL) was heated to 80 ° C. with stirring, and a reaction was performed for about 4 hours. The disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. When the NCO peak disappeared, it was regarded as the end point of the reaction. After the reactant was cooled to room temperature, it was filtered through a 100-mesh filter cloth to obtain an elastomer A having a butadiene structure and a phenolic hydroxyl group (nonvolatile 50% by mass). The number average molecular weight is 5,500.

    [Synthesis example 2]         <Manufacture of Elastomer B>    

In a flask equipped with a stirring device, a thermometer and a condenser, 292.09 g of diethylene glycol ether acetate as a solvent and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by Exxon Mobil Co., Ltd.) were charged. 100.1 g (0.4 mole) of phenylmethane diisocyanate and 426.6 g (0.2 mole) of polybutadiene glycol (hydroxyl value 52.6 KOH-mg / g, molecular weight 2133) were reacted at 70 ° C for 4 hours. Next, 195.9 g (0.2 mol) of nonylphenol novolak resin (229.4 g / eq hydroxyl group, 4.27 functional average, 979.5 g / mole average calculated molecular weight) and ethylene glycol bistrimellitic anhydride (ethylene glycol bisanhydrotrimellitate) 41.0 g (0.1 mol), the temperature was raised to 150 ° C. over 2 hours, and the reaction was allowed to proceed for 12 hours.

After the reaction, a polyimide resin solution having a transparent brown liquid, non-volatile content of 55%, and a viscosity of 14 Pa · s (25 ° C) can be obtained. The obtained solution of the polyimide resin was coated on a KBr plate, and the infrared absorption spectrum of the sample after the solvent component was volatilized was measured. As a result, it was confirmed that the characteristic absorption of isocyanate group at 2270 cm ^-1 completely disappeared, and The absorption of the pyrimide ring at 725 cm ^-1 and 1780 cm ^-1 and 1720 cm ^{-1 was} confirmed. In addition, absorption of a urethane bond at 1540 cm ^{-1 was} confirmed. In addition, the amount of carbon dioxide produced as a result of the imidization of sulfonium was traced to 8.8 g (0.2 mol) based on the change in the weight of the flask. The functional anhydride equivalent of ethylene glycol bistrimellitic anhydride is 0.2 mol, and the amount of carbon dioxide produced is also 0.2 mol. All anhydrides are used for the formation of ammonium imine, so it is concluded that there is no carboxylic anhydride. According to this, the 0.2 mol portion of the isocyanate group is converted into a fluorene imine bond, and the remaining isocyanate group forms an amine group with the hydroxyl group of the polybutadiene glycol and the phenolic hydroxyl group in the nonylphenol novolac resin. The formate bond is based on the conclusion that a phenolic hydroxyl group having a phenol novolac resin in the resin is obtained, and a part of the phenolic hydroxyl group is a polyfluorene imine formic acid modified by a urethane bond. Ester resin.

    [Example 1]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 30 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 288 g / eq), 8 parts, amino phenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent: 90 ~ 105g / eq) 5 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, elastomer A (50% solid content, number average molecular weight) : 5500) 300 parts, cresol novolac resin ("KA-1163" manufactured by DIC Corporation, phenolic hydroxyl equivalent: 118 g / eq), 12 parts, SO-C4 (via aminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) "KBM573") 740 parts of spherical silicon dioxide (manufactured by Admatechs Co., Ltd., average particle size: 1 μm)) and 35 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to produce a resin varnish.

    [Example 2]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 30 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 288 g / eq), 8 parts, amino phenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent: 90 ~ 105g / eq) 5 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, elastomer B272 part, cresol novolac resin (DIC "KA-1163" manufactured by the company, 12 parts of phenolic hydroxyl equivalent: 118g / eq, SO-C4 (aluminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) Admatechs Corporation (average particle size: 1 μm)) 950 parts and methyl ethyl ketone 45 parts, and uniformly dispersed using a high-speed rotary mixer to produce a resin varnish.

    [Example 3]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 30 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 288 g / eq), 8 parts, amino phenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent: 90 ~ 105g / eq) 5 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, elastomer B272 part, cresol novolac resin (DIC "KA-1163" manufactured by the company, 12 parts of phenolic hydroxyl equivalent: 118g / eq, SO-C4 (aluminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) Admatechs Co., Ltd., average particle size 1 μm)) 1070 parts and methyl ethyl ketone 50 parts, and uniformly dispersed using a high-speed rotary mixer to produce a resin varnish.

    [Comparative Example 1]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 40 parts, biphenyl epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 61 parts, naphthalene epoxy resin ("HP4710" manufactured by DIC Corporation, epoxy equivalent 160 ~ 180g / eq) 20 parts, aminophenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 ~ 105g / eq) 13 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., 1 -1 part of benzyl-2-phenylimidazole), 40 parts of polyester resin (manufactured by Unitika, "UE3400"), cresol novolac resin ("KA-1163" manufactured by DIC, phenolic hydroxyl equivalent: 118 g / eq) 30 parts, 950 parts of SO-C4 (spherical silica (manufactured by Admatechs, average particle size: 1 μm)) surface treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and 40 parts of ethyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

    [Comparative Example 2]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 40 parts, biphenyl epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 288 g / eq), 61 parts, naphthalene epoxy resin ("HP4710" manufactured by DIC Corporation, epoxy equivalent 160 ~ 180g / eq) 20 parts, aminophenol type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 ~ 105g / eq) 13 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Co., 1 -1 part of benzyl-2-phenylimidazole), 40 parts of polyester resin (manufactured by Unitika, "UE3400"), cresol novolac resin ("KA-1163" manufactured by DIC, phenolic hydroxyl equivalent: 118 g / eq) 30 parts, SO-C4 (spherical silica (manufactured by Admatechs, average particle size: 1 μm)) surface treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and 200 parts 30 parts of ethyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare a resin varnish.

    [Comparative Example 3]    

Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., 1: 1 mixed product (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent weight: 169 g / eq) 31 parts, 23 parts of bisphenol A novolac epoxy resin ("157S70" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200-220 g / eq), naphthalene epoxy resin ("HP4710" manufactured by DIC Corporation, Oxygen equivalent 160 ~ 180g / eq) 20 parts, polyester resin (Unitika, "UE3400") 4 parts, cresol novolac resin ("KA-1163" manufactured by DIC, phenolic hydroxyl equivalent: 118g / eq) 24 parts, 640 parts of SO-C4 (spherical silicon dioxide (manufactured by Admatechs, average particle size: 1 μm)) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), hardening accelerator ( 1 part of "1B2PZ", 1-benzyl-2-phenylimidazole, and 30 parts of methyl ethyl ketone manufactured by Shikoku Chemical Co., Ltd. were uniformly dispersed using a high-speed rotary mixer to produce a resin varnish.

The abbreviations and the like in the following tables are as follows.

UE3400: Polyester resin, manufactured by Unitika

ZX1059: 1: 1 mixture (mass ratio) of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent weight: 169g / eq, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.

630LSD: Aminophenol epoxy resin, epoxy equivalent: 90 ~ 105g / eq, manufactured by Mitsubishi Chemical Corporation

NC3000H: Biphenyl epoxy resin, epoxy equivalent: 288g / eq, manufactured by Nippon Kayaku Co., Ltd.

HP4710: Naphthalene-type epoxy resin, manufactured by DIC Corporation, epoxy equivalent 160 ~ 180g / eq

157S70: Bisphenol A novolac epoxy resin, made by Mitsubishi Chemical Corporation, epoxy equivalent: 200 ~ 220g / eq

SO-C4: Spherical silicon dioxide (manufactured by Admatechs Co., Ltd., average particle size 1 μm) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)

KA-1163: Cresol novolac resin, phenolic hydroxyl equivalent: 118g / eq, manufactured by DIC Corporation

1B2PZ: 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Co., Ltd.

(c) Ingredient content: The content (mass%) when the non-volatile content of the resin composition is set to 100% by mass.

(a) Component content: The content (mass%) when the non-volatile content of the resin composition after removing the component (c) is set to 100% by mass.

    [Production example 1]         <Production of Fan-out WLP resin sheet>    

On the polyethylene terephthalate film (thickness: 38 μm), the resin varnish described in Example 1 was applied with a die coater so that the thickness of the dried resin composition layer was 200 μm, and the resin varnish described in Example 1 was applied at 80 to 120. It dried at 10 degreeC (average 100 degreeC) for 10 minutes, and obtained the resin sheet.

When the above-mentioned resin sheet was used to produce the sealing layer of the Fan-out WLP shown in FIG. 3, it was found that it had sufficient performance as a Fan-out WLP.

Claims (14)

    A resin composition comprising (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 resin composition is characterized in that when the non-volatile content of the resin composition is set to 100% by mass, the content of the component (c) is 50% to 95% by mass, and the resin composition is heat cured at 180 ° C for 1 hour. The elasticity of the obtained hardened product at 23 ° C is 18 GPa or less, and the specific permittivity of the hardened product at 23 ° C and a measurement frequency of 5.8 GHz is 3.5 or less, and the specific dielectric of the hardened product at 23 ° C and a measurement frequency of 1 GHz. The difference in the ratio is 0.3 or less.         For example, the resin composition of claim 1, wherein the dielectric tangent of the cured product obtained by thermally curing the resin composition at 180 ° C. for 1 hour at 23 ° C. and a measurement frequency of 5.8 GHz is 0.01 or less, and the cured product is at 23 ° The difference between the dielectric tangent at ℃ and the measurement frequency of 1 GHz is 0.002 or less.         For example, in the resin composition of claim 1, when the non-volatile content of the resin composition after removing the component (c) is set to 100% by mass, the content of the component (a) is 30% to 85% by mass.         The resin composition according to claim 1, wherein the component (a) has a structural unit selected from butadiene, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, and an alkyleneoxy group. One or more types of structural units, structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units.         The resin composition according to claim 1, wherein the component (a) is one or more selected from a resin having a glass transition temperature of 25 ° C or lower and a resin in a liquid state at 25 ° C.         For example, the resin composition of claim 1, wherein the component (a) has a functional group capable of reacting with the component (b1) and the component (b2).         The resin composition according to claim 1, wherein the component (a) has a phenolic hydroxyl group.         The resin composition according to claim 1, further comprising (d) a curing agent selected from the group consisting of a phenol-based curing agent and an active ester curing agent.         The resin composition of claim 1 is a resin composition for an insulating layer of a semiconductor wafer package.         A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 9.         The resin sheet according to claim 10 is a resin sheet for an insulating layer of a semiconductor wafer package.         A circuit board characterized by comprising an insulating layer formed of a hardened body of the resin composition according to any one of claims 1 to 9.         A semiconductor wafer package is characterized in that a semiconductor wafer is mounted on a circuit substrate of claim 12.         A semiconductor wafer package comprising a semiconductor wafer sealed with a resin composition according to any one of claims 1 to 9 or a resin sheet according to claim 10.