TW201920340A - Resin composition - Google Patents

Abstract

Provided is a resin composition which has a low coefficient of thermal expansion, can restrict bending, obtains a hardened object with a high contact force even though being repeatedly heated and cooled, and further, has excellent compression molding properties. According to the present invention the resin composition comprises: (A) epoxy resin having viscosity less than 20 Pa.s at 45 DEG C and an alkene frame in a molecule; (B) an inorganic charging material; and (C) a hardening agent.

Description

Resin composition

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

In recent years, the demand for small, high-performance electronic devices such as smart phones and tablet devices has increased greatly. With this, the insulating layer for semiconductor chip packages used in these small electronic devices has also been required to be higher. High performance. As such an insulating layer, for example, a resin composition is hardened and formed (refer to, for example, Patent Documents 1 and 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-55233 [Patent Document 2] International Publication No. 2014/157446

[Problems to be Solved by the Invention]

In order to reduce the loss of electrical signals, the dielectric tangent is required to be low for the insulating layer. As a result of this investigation, the present inventors have found that by using a resin composition comprising an epoxy resin having an olefin skeleton in the molecule, an insulating layer having a low dielectric tangent can be obtained. However, as a result of further investigations by the present inventors, it was found that the resin composition made of an epoxy resin having an olefin skeleton in the molecule has a low compression moldability. When a resin composition layer having a low compression moldability is to be formed by a compression molding method, it is difficult to fill the resin composition in each corner.

In addition, in recent years, smaller semiconductor chip packages have been required, and therefore, the insulating layer for semiconductor chip packages has been required to be thinner. Therefore, development of an insulating layer having a low coefficient of thermal expansion (CTE, also referred to as a "coefficient of thermal expansion") and low warpage can be expected. Further, the insulation layer is required to obtain high adhesion even after repeated heating and cooling. For example, it is required that the insulation layer that is in close contact with the silicon wafer is difficult to be insulated even after repeated heating and cooling. Peel off the silicon wafer. However, when a conventional resin composition made of an epoxy resin having an olefin skeleton in the molecule is included, satisfactory performance cannot be achieved in the evaluation of online thermal expansion coefficient, warpage, and adhesion.

The resin composition used to form the insulating layer is considered to also be used as a sealing material for a semiconductor wafer package. For example, in a semiconductor wafer package, as a sealing layer which seals a semiconductor wafer, it is thought that the hardened | cured material obtained by hardening a resin composition can be used. Even when the resin composition is used as a sealing material for a semiconductor wafer package, the same problems as described above occur.

The present invention is an invention proposed in view of the foregoing problems, and an object of the present invention is to provide a resin composition which can obtain a cured product as described below and has excellent compression moldability. The cured product has a linear thermal expansion coefficient of Low, can suppress warping, can obtain high adhesion even after repeated heating and cooling; a resin sheet having a resin composition layer, the resin composition layer comprising the aforementioned resin composition; a circuit including an insulating layer The substrate, wherein the insulating layer is formed by the hardened product of the aforementioned resin composition; and a semiconductor chip package comprising the hardened product of the aforementioned resin composition. [Means for solving problems]

As a result of intensive research in order to solve the aforementioned problems, the present inventors found that by including (A) an epoxy resin having a specified range of viscosity at 45 ° C and an olefin skeleton in the molecule, (B) an inorganic filler, and (C) A resin composition composed of a combination of hardeners can solve the aforementioned problems, and thus completed the present invention. That is, the present invention includes the following inventions.

[1]. A resin composition comprising: (A) an epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C. and having an olefin skeleton in the molecule, (B) an inorganic filler, and (C) a hardener . [2]. The resin composition according to [1], wherein the component (A) has a polybutadiene structure in a molecule. [3]. The resin composition according to [1] or [2], wherein the viscosity of the component (A) at 45 ° C. is 15 Pa · s or less. [4]. The resin composition according to any one of [1] to [3], wherein the content of the component (A) is 0.2% by mass to 10% by mass relative to 100% by mass of the nonvolatile component of the resin composition. %. [5]. The resin composition according to any one of [1] to [4], wherein the average particle diameter of the component (B) is 0.1 μm to 10 μm. [6]. The resin composition according to any one of [1] to [5], wherein the component (C) is an acid anhydride-based hardener or a phenol-based hardener. [7]. The resin composition according to any one of [1] to [6], further including (D) an epoxy resin other than the (A) component. [8]. The resin composition according to any one of [1] to [7], further comprising (E) a hardening accelerator. [9]. The resin composition according to any one of [1] to [8], which is a resin composition for semiconductor sealing or an insulating layer. [10]. The resin composition according to any one of [1] to [9], which is a liquid resin composition. [11]. A resin sheet comprising: a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [10]. [12]. A circuit board including an insulating layer formed by a cured product of the resin composition according to any one of [1] to [10]. [13]. A semiconductor wafer package comprising: the circuit board according to [12] and a semiconductor wafer mounted on the circuit board. [14]. A semiconductor wafer package comprising: a semiconductor wafer and a cured product of the resin composition according to any one of [1] to [10], wherein the semiconductor wafer is sealed. [Effect of the invention]

According to the present invention, it is possible to provide a resin composition which can obtain a hardened material having excellent compression moldability as described below. The hardened material has a low coefficient of linear thermal expansion, can suppress warpage, and can be subjected to repeated heating and heating. High adhesion can also be obtained by cooling; a resin sheet having a resin composition layer containing the aforementioned resin composition; a circuit board including an insulating layer, wherein the insulating layer is formed by the aforementioned Formed by a cured product of a resin composition; and a semiconductor wafer package comprising the cured product of the aforementioned resin composition.

[Best Mode for Implementing Invention]

The following are examples and examples, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily changed and implemented without departing from the scope of the patent application of the present invention and its equivalent range.

In the following description, the "resin component" of the resin composition means a component from which the inorganic filler is removed from the non-volatile components contained in the resin composition.

[1. Overview of resin composition] The resin composition of the present invention includes: (A) an epoxy resin having a specified range of viscosity at 45 ° C and an olefin skeleton in the molecule; (B) an inorganic filler; and (C) )hardener. In the following description, the "(A) epoxy resin which has a viscosity in a specified range at 45 ° C and has an olefin skeleton in the molecule" as the component (A) is sometimes referred to as "(A) epoxy resin".

By combining and including the aforementioned (A) component, (B) component, and (C) component, the following desired effects of the present invention can be obtained: "The resin composition is excellent in compression moldability and can obtain linear thermal expansion. A hardened product that has a low coefficient, suppresses warping, and exhibits high adhesion even after repeated heating and cooling. " The cured product of this resin composition exhibits excellent characteristics, and can be preferably used as an insulating layer and a sealing material of a semiconductor wafer package.

Moreover, the said resin composition system can further combine arbitrary components and include them in (A) component, (B) component, and (C) component. Examples of the optional component include (D) an epoxy resin other than (A) an epoxy resin, and (E) a curing accelerator.

[2. (A) Epoxy resin] (A) Epoxy resin has a viscosity in a specified range at 45 ° C. (A) The specific viscosity of the epoxy resin at 45 ° C. is generally 20 Pa · s or less, preferably 15 Pa · s or less, still more preferably 10 Pa · s or less, and particularly preferably 6.0 Pa · s or less. By using the (A) epoxy resin having such a viscosity, the compression moldability of the resin composition can be improved. Furthermore, by using such a viscosity (A) epoxy resin, the hardened | cured material which has a low linear thermal expansion coefficient, can suppress a warp, and exhibits high adhesiveness even by repeated heating and cooling can be obtained. (A) The lower limit of the viscosity of the epoxy resin at 45 ° C is not particularly limited, and may be, for example, 1 Pa · s or more, 2 Pa · s or more, 3 Pa · s or more.

(A) The viscosity of an epoxy resin can be measured by the measuring method as described in an Example.

The (A) epoxy resin has an olefin skeleton in the molecule. Here, the so-called olefin skeleton is a structure represented by the following formula (1). The front-end atom bonded to the carbon atom bonding portion represented by the formula (1) is not particularly limited, but is generally a hydrogen atom or a carbon atom. By using the (A) epoxy resin which has such an olefin skeleton, the dielectric tangent of the hardened | cured material of a resin composition can generally be reduced. Furthermore, it is generally possible to improve the insulation of the cured product or reduce the hygroscopicity.

(A) Epoxy resins may have an olefin skeleton on the main chain of the molecule, an olefin skeleton on the side chain of the molecule, or an olefin skeleton on both the main chain and the side chain of the molecule. . Among these, from the viewpoint of obtaining the desired effect of the present invention significantly and effectively reducing the dielectric tangent of the cured product, it is preferable to have an olefin skeleton on the side chain of the molecule.

The (A) epoxy resin having an olefin skeleton generally contains a structural unit having an olefin skeleton in its molecule. As the structural unit, a divalent hydrocarbon group having an olefin skeleton is preferred, and an olefin skeleton is preferred from the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product. The divalent aliphatic hydrocarbon group is more preferable, and a divalent chain aliphatic hydrocarbon group having an olefin skeleton is particularly preferable.

The number of carbon atoms in the aforementioned structural unit having an olefin skeleton is preferably 2 or more from the viewpoint of remarkably obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the hardened material. 3 or more, particularly preferably 4 or more, preferably 10 or less, and still more preferably 8 or less, and particularly preferably 6 or less.

In particular, from the viewpoint of remarkably obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product, the aforementioned structural unit having an olefin skeleton preferably contains an alkenyl group. The number of carbon atoms of the alkenyl group is generally 2 or more, preferably 6 or less, and more preferably from the viewpoint of obtaining the desired effect of the present invention significantly and from the viewpoint of effectively reducing the dielectric tangent of the hardened material. It is 4 or less, and particularly preferably 3 or less. Examples of such an alkenyl group include a vinyl group, a 1-propenyl group, and a 2-propenyl group.

As said structural unit which has an olefin skeleton, as a preferable example, the structural unit represented by following formula (2) or formula (3) is mentioned. Both the structural unit represented by formula (2) and the structural unit represented by formula (3) can be formed by polymerization of butadiene. Specifically, the structural unit represented by the formula (2) is a structural unit that can be formed by 1,2-addition polymerization of butadiene. The structural unit represented by the formula (3) is a structural unit that can be formed by 1,4-addition polymerization of butadiene. Among them, the structural unit represented by the formula (2) is preferable from the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the hardened material.

(A) The number of the aforementioned structural units having an olefin skeleton contained in the molecule of the epoxy resin may be one, or may be two or more. From the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product, (A) the epoxy resin preferably contains two or more of the aforementioned olefin skeletons in the molecule. Construct units as repeating units.

In particular, (A) an epoxy resin is preferable to have a polybutadiene structure in the molecule from the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product. . The so-called polybutadiene structure refers to a structure that can polymerize and form butadiene. Specific examples of the polybutadiene structure include a structure including two or more structural units selected from the structural unit represented by the formula (2) and the structural unit represented by the formula (3) in one molecule. . Among them, the epoxy resin is preferably a structural unit represented by Formula (2) containing two or more molecules in one molecule.

Furthermore, in each molecule of the epoxy resin (A), the number of structural units represented by the formula (2) is more than the number of structural units represented by the formula (3). Thereby, the effect desired by this invention can be acquired remarkably, especially the compression moldability of a resin composition can be improved effectively, and the adhesiveness of hardened | cured material at the time of repeated heating and cooling can be improved effectively.

The (A) epoxy resin generally has an epoxy group. (A) Epoxy resins may have an epoxy group on the main chain of the molecule, an epoxy group on the side chain of the molecule, or both of the main chain and the side chain of the molecule. Epoxy. Among them, from the viewpoint of significantly obtaining the desired effect of the present invention and from the viewpoint of effectively reducing the dielectric tangent of the cured product, it is preferable to have an epoxy group on the side chain of the molecule.

(A) The epoxy resin may have an epoxy group in the aforementioned structural unit having an olefin skeleton, but from the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product In other words, it is preferable to have an epoxy group in a structural unit different from the aforementioned structural unit having an olefin skeleton.

The number of carbon atoms in the aforementioned structural unit having an epoxy group is preferably 2 or more from the viewpoint of remarkably obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product. It is 3 or more, particularly preferably 4 or more, preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less.

As said structural unit which has an epoxy skeleton, the structural unit represented by following formula (4) or formula (5) is mentioned as a preferable example. The structural unit represented by the formula (4) can be formed by, for example, epoxidizing a polybutadiene containing the structural unit represented by the formula (2). The structural unit represented by the formula (5) can be formed by, for example, epoxidizing a polybutadiene containing the structural unit represented by the formula (3). Among them, the structural unit represented by the formula (4) is preferable from the viewpoint of significantly obtaining the desired effect of the present invention and the viewpoint of effectively reducing the dielectric tangent of the cured product.

Furthermore, in each molecule of the epoxy resin (A), the number of structural units represented by the formula (4) is more than the number of structural units represented by the formula (5). Thereby, the effect desired by this invention can be acquired remarkably, especially the compression-moldability of a resin composition can be improved effectively, and the adhesiveness of the hardened | cured material at the time of repeated heating and cooling can be improved effectively.

(A) It is preferable that an epoxy resin has two or more epoxy groups in a molecule | numerator from a viewpoint of obtaining the effect which the present invention expects remarkably. Moreover, (A) epoxy resin is an aliphatic epoxy resin which does not contain an aromatic ring in a molecule | numerator from a viewpoint which can obtain the effect which the present invention expects remarkably.

When an example of the molecular structure of the epoxy resin (A) is given, for example, one represented by the formula (6) can be cited. In formula (6), m and n each independently represent a natural number.

As a specific example of (A) epoxy resin, "JP400" made by Soda Co., Ltd. which has a molecular structure represented by the said Formula (6) is mentioned. Moreover, (A) component system can be used individually by 1 type, or can be used combining 2 or more types by arbitrary ratios.

In general, epoxy resins can be classified into epoxy resins that are liquid at 20 ° C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20 ° C ( Sometimes called "solid epoxy resin"). (A) The epoxy resin may be a solid epoxy resin, but a liquid epoxy resin is preferred. When (A) the epoxy resin is a liquid epoxy resin, the compression moldability of the resin composition can be effectively improved, and the adhesiveness of the hardened material during repeated heating and cooling can be effectively improved.

(A) The number average molecular weight Mn of the epoxy resin is preferably 2500 or more, more preferably 3,000 or more, particularly preferably 3200 or more, preferably 5500 or less, still more preferably 5,000 or less, and particularly preferably 4,000 or less. When the number average molecular weight Mn of the (A) epoxy resin is at least the lower limit of the aforementioned range, the compression moldability of the resin composition can be improved, or the linear thermal expansion coefficient of the hardened product of the resin composition can be effectively reduced, Or it can effectively improve the ability to suppress the hardened | cured material which warp, or can effectively suppress the peeling of the hardened | cured material by heating and cooling. In addition, when the number average molecular weight Mn of the (A) epoxy resin is equal to or less than the upper limit of the foregoing range, the compression moldability of the resin composition can be improved, or the linear thermal expansion of the cured product of the resin composition can be effectively reduced. The coefficient or the toughness of the hardened material of the resin composition can be improved to effectively suppress the occurrence of cracks.

(A) The weight-average molecular weight Mw of the epoxy resin is preferably 5,000 to 60,000, more preferably 6,000 to 50,000, and even more preferably 7,000 to 20,000 from the viewpoint of remarkably obtaining the desired effect of the present invention.

The number average molecular weight Mn and the weight average molecular weight Mw of the resin can be measured in terms of polystyrene by gel permeation chromatography (GPC) method. For example, the number average molecular weight Mn and weight average molecular weight Mw of the resin can be LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko Corporation as a column. 804L, chloroform or the like as a mobile phase, was measured at a column temperature of 40 ° C, and was calculated using a calibration curve of standard polystyrene.

(A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, more preferably 80 to 2000, and still more preferably 110 to 1,000. When the epoxy equivalent of the (A) epoxy resin is in the aforementioned range, an insulating layer having a higher cross-link density and a smaller surface roughness of the cured product of the resin composition can be obtained. The epoxy equivalent is the mass of a resin containing one equivalent of an epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(A) The glass transition temperature of the epoxy resin is preferably -20 ° C or lower, further preferably -30 ° C or lower, particularly preferably -40 ° C or lower, preferably -90 ° C or higher, and still more preferably -80. Above 70 ° C, particularly preferably above -70 ° C. When the (A) epoxy resin has a glass transition temperature within the aforementioned range, the desired effect of the present invention can be significantly obtained.

The amount of the (A) epoxy resin in the resin composition is preferably 0.2% by mass or more with respect to 100% by mass of the nonvolatile matter in the resin composition from the viewpoint that the desired effect of the present invention is significantly obtained. It is more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, preferably 10% by mass or less, still more preferably 9.5% by mass or less, and particularly preferably 9% by mass or less. In addition, generally, by concentrating the amount of the (A) epoxy resin within the aforementioned range, the dielectric tangent of the cured product of the resin composition can be reduced.

[3. (B) Inorganic Filler] The resin composition system contains an inorganic filler as the (B) component. By using the (B) inorganic filler, the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced, and warpage can be suppressed.

As the material of the (B) inorganic filler, an inorganic compound is used. Examples of the material of the (B) inorganic filler include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and water. Aluminum ore, 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, Bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate tungstate. Among these, silicon dioxide is particularly suitable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. Further, as the silicon dioxide system, spherical silicon dioxide is preferable. (B) The inorganic fillers may be used alone or in combination of two or more at any ratio.

In general, (B) the inorganic filler is contained in the resin composition in a state of particles. (B) The average particle size of the inorganic filler is preferably 0.1 μm or more, more preferably 0.5 μm or more, particularly preferably 1.0 μm or more, preferably 10 μm or less, and still more preferably 8.0 μm or less, and particularly preferably 5.0 μm or less. When the average particle diameter of the (B) inorganic filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained. In particular, when the average particle diameter of the (B) inorganic filler is equal to or less than the upper limit of the aforementioned range, the compression moldability of the resin composition can be effectively improved and flow marks can be reduced. Moreover, the adhesiveness of the hardened | cured material at the time of repeated heating and cooling can be improved effectively. In addition, since the average particle diameter of the (B) inorganic filler is in the aforementioned range, generally, when an insulating layer is formed using a cured product of a resin composition, the surface roughness of the insulating layer can be reduced.

(B) The average particle diameter of particles such as an inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the average particle diameter can be measured from the particle size distribution as the average particle diameter. As the measurement sample, a particle in which a particle is dispersed in water or the like by ultrasonic waves is preferably used. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd. can be used.

Examples of the (B) inorganic filler as described above include "MSS-6" and "AC-5V" manufactured by Ronson; "SP60-05" and "SP507-05" manufactured by Nippon Steel-Sumikin Materials. ; "YC100C", "YA050C", "YA050C-MJE", "YA010C" by Admatechs; "UFP-30", "SFP-130MC", "FB-7SDC", "FB-5SDC", "FB-5SDC", " "FB-3SDC"; "Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO" manufactured by Admatechs Corporation -C1 "," FE9 ", etc.

(B) The inorganic filler is preferably surface-treated with an appropriate surface-treating agent. The surface treatment can improve the moisture resistance and dispersibility of the (B) inorganic filler. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane coupling agent, a silane-based coupling agent, an alkoxysilane compound, and a silicone Azuran compounds, titanate-based coupling agents, and the like.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM403" (3-glycidyloxypropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Oxysilane), Shin-Etsu Chemical Industry Company "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Industry Company "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Industry "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by the company, "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., Shin-Etsu "SZ-31" (hexamethyldisilazane) manufactured by Chemical Industries, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, and "KBM-4803" (long-chain ring) manufactured by Shin-Etsu Chemical Industries Oxysilane coupling agent). Among them, a silane coupling agent containing a nitrogen atom is preferred, an amine-based silane coupling agent containing a phenyl group is even more preferred, and N-phenyl-3-aminoalkyltrimethoxysilane is more preferred, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane are more preferred. The surface treatment agent may be used singly or in combination of two or more kinds at an arbitrary ratio.

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 (B) inorganic filler. (B) The carbon content per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, and more preferably 0.1 mg / m ² or more from the viewpoint of improving the dispersibility of the inorganic filler. Particularly preferred is 0.2 mg / m ² or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, the aforementioned carbon content is preferably 1 mg / m ² or less, and more preferably 0.8 mg / m ² Below, particularly preferred is 0.5 mg / m ² or less.

(B) The carbon content per unit surface area of the inorganic filler can be washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as "MEK")), and the inorganic filler (B) after surface treatment can be washed. The net treatment was subsequently determined. Specifically, a sufficient amount of methyl ethyl ketone was mixed with the (B) inorganic filler subjected to surface treatment with a surface treatment agent, and then ultrasonically washed at 25 ° C. for 5 minutes. After removing the upper liquid and drying the solid content, the carbon content per unit surface area of the (B) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of the (B) inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and more preferably 70% by mass relative to 100% by mass of the nonvolatile matter in the resin composition. % Or more, more preferably 95% by mass or less, still more preferably 90% by mass or less, and still more preferably 86% by mass or less. When the amount of the (B) inorganic filler is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and in particular, the linear thermal expansion coefficient of the resin composition can be effectively reduced.

[4. (C) Hardener] The resin composition system contains a hardener as the component (C). (C) The hardener system generally has a function of reacting with epoxy resins such as (A) epoxy resin and (D) epoxy resin to harden the resin composition. (C) A hardener may be used individually by 1 type, or may be used combining two or more types by arbitrary ratios.

As the (C) curing agent, a compound that can react with an epoxy resin to harden the resin composition can be used, and examples thereof include an acid anhydride-based hardener, a phenol-based hardener, an active ester-based hardener, and a cyanate-based hardener. , Benzoxazine-based hardener, carbodiimide-based hardener, etc. Among them, an acid anhydride-based hardener and a phenol-based hardener are preferred from the viewpoint of remarkably obtaining the effects of the present invention.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic acid. Dicarboxylic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2,5-dioxotetrahydro-3- Furan) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromelite dianhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, Naphthalene tetracarboxylic dianhydride, oxophthalic anhydride, 3,3'-4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro -5- (tetrahydro-2,5-dioxo-3-furan) -naphthalene [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), Polymeric anhydrides, such as styrene and maleic resin, copolymerized with styrene and maleic acid.

Examples of the phenol-based curing agent include a curing agent having one or more hydroxyl groups bonded to an aromatic ring (a benzene ring, a naphthalene ring, etc.) in one molecule, and preferably having two or more. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. From the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolac structure is preferred. From the viewpoint of adhesion, a nitrogen-containing phenol-based hardener is more preferred, and a triazine skeleton-containing phenol-based hardener is more preferred. In particular, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance, and adhesion.

Specific examples of the phenol-based hardener and naphthol-based hardener include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd .; "NHN", "CBN", "GPH" made by the company; "SN-170", "SN-180", "SN-190", "SN-475", "SN-475" made by Nippon Steel & Sumitomo Chemical Co., Ltd. 485 "," SN-495 "," SN-495V "," SN-375 "," SN-395 ";" TD-2090 "," TD-2090-60M "," LA-7052 "made by DIC Corporation , "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163" "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75", etc., manufactured by Qunrong Chemical Co., Ltd.

Examples of the active ester-based hardener include hardeners having one or more active ester groups in one molecule. Among them, as the active ester-based hardener, phenol esters, thiophenol esters, N-hydroxylamine esters, and heterocyclic hydroxyl compounds, etc., are esters having two or more reactivity in one molecule. A compound based on a base is preferred. The active ester-based hardener is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improvement in heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is preferable. A hardening agent is more preferred.

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, and methylformate. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, pyrogallol, dicyclopentadiene type diphenol compound, phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include 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 a phenol novolac, An active ester compound comprising a benzamidine compound of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure formed from phenylene-dicyclopentyl-phenylene.

Examples of commercially available active ester hardeners include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC-8000" as active ester compounds containing a dicyclopentadiene-type diphenol structure. 8000H "," HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC Corporation); structure including naphthalene "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetic acid compound of phenol novolac; benzoic acid compound containing phenol novolac "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener for acetic acid compounds of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. as the active ester hardener.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 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, etc. Bifunctional cyanate resin; polyfunctional cyanate resin derived from phenol novolac and cresol novolac; prepolymers obtained by triazinating a part of these cyanate resins. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (both are phenol novolac-type polyfunctional cyanate resins) and "ULL-950S" (multifunctional cyanide resins) manufactured by LONZA Japan. Ester resin); "BA230", "BA230S75" (a part or all of the bisphenol A dicyanate is triazinated to form a tripolymer) and the like.

Specific examples of the benzoxazine-based hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

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

(C) The content of the component is, from the viewpoint of obtaining the desired effect of the present invention significantly, preferably 1 mass% or more, and more preferably 5 mass%, with respect to 100 mass% of the resin component in the resin composition. The above is more preferably 10% by mass or more, more preferably 70% by mass or less, still more preferably 65% by mass or less, and still more preferably 60% by mass or less.

When the epoxy group number of the epoxy resin containing (A) epoxy resin and (D) epoxy resin is set to 1, the active group number of (C) hardener is preferably 0.1 or more, and more preferably 0.2 or more, more preferably 0.3 or more, preferably 2 or less, still more preferably 1.8 or less, more preferably 1.6 or less, and particularly preferably 1.4 or less. Here, the "epoxy number of an epoxy resin" means the total value which divided the mass of the non-volatile matter of the epoxy resin which exists in a resin composition by the epoxy equivalent value. The "number of active groups of (C) hardener" refers to the total value obtained by dividing the mass of the nonvolatile component of (C) hardener present in the resin composition by the value of the equivalent of the active group. When the epoxy group number of the epoxy resin is set to 1 and the active group number of the (C) hardener is in the aforementioned range, the desired effect of the present invention can be significantly obtained, and further, the heat resistance of the hardened product of the general resin composition layer can be obtained. For more promotion.

[5. (D) Arbitrary epoxy resin] As an arbitrary component, the resin composition system may include (D) epoxy resin other than the above (A) epoxy resin. Examples of the (D) epoxy resin include bixylenol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol. AF epoxy resin, dicyclopentadiene epoxy resin, trihydric phenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol ring Oxygen resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiral ring, cyclohexane epoxy resin Resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. The epoxy resin can be used singly or in combination of two or more kinds.

Among the resin compositions, the epoxy resin (D) is preferably an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is based on 100% by mass of the nonvolatile content of the (D) epoxy resin. It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The (D) epoxy resin may be a liquid epoxy resin, a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, from the viewpoint of improving the compression moldability of the resin composition, it is preferable to use a liquid epoxy resin as the (D) epoxy resin.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

The liquid epoxy resins are bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, and glycidylamine epoxy resin. Epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, aliphatic epoxy resin, and butyl epoxy resin Diene-structured epoxy resins are preferred, and bisphenol A-type epoxy resins, glycidylamine-type epoxy resins, and aliphatic epoxy resins are more preferred.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC; and "EXA-850CRP" (bisphenol A type) manufactured by DIC Epoxy resin); "828US", "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) made by Mitsubishi Chemical Corporation; "jER807", "1750" (double Phenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) made by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine type epoxy resin) made by Mitsubishi Chemical Corporation; Mitsubishi Chemical "YED-216D" (aliphatic epoxy resin) manufactured by the company; "ZX1059" (mixed product of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd .; Nissin "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Tetsujukin Chemical Co., Ltd .; "EX-721" (glycidyl ester epoxy resin) manufactured by Nagasechemtex; "CELOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by DAICEL; "PB-3" manufactured by DAICEL 600 "(epoxy resin with butadiene structure);" EP-3980S "(glycidylamine type epoxy resin) made by ADEKA;" ELM-100H "(glycidylamine type epoxy resin) made by Sumitomo Chemical Co., Ltd. Resin) and so on. These systems can be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and an aromatic solid having three or more epoxy groups in one molecule. Shaped epoxy resins are also preferred.

As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, Phenolic epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, dnaphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF epoxy resin Resins and tetraphenylethane epoxy resins are preferred, and bixylenol epoxy resins, naphthalene epoxy resins, bisphenol AF epoxy resins, and dnaphthyl ether epoxy resins are more preferred. good.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); "N-690" (cresol novolac-type epoxy resin) manufactured by DIC; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC; "HP- 7200 "(dicyclopentadiene epoxy resin);" HP-7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "made by DIC Corporation , "EXA-7311-G4S", "HP6000" (Danaphthyl ether type epoxy resin); "EPPN-502H" (trihydric phenol type epoxy resin) made by Nippon Kayaku Co .; "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthalene type epoxy resin) made by Nippon Steel; "ESN485" (naphthol novolac type epoxy resin) made by Nippon Steel & Sumitomo Chemical Co., Ltd .; "YX4000H", "YX4000" made by Mitsubishi Chemical Corporation, "YL6121" (biphenyl epoxy resin); "YX4000HK" (bixylenol epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene epoxy resin) manufactured by Mitsubishi Chemical Corporation; OSAKA Gas chemical company "PG-100" and "CG-500" made by Mitsubishi Chemical; "YL7760" (bisphenol AF type epoxy resin) made by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) made by Mitsubishi Chemical Corporation; Mitsubishi Chemical "JER1010" (solid bisphenol A type epoxy resin) manufactured by the company; "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.

As the (D) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, these amount ratios (liquid epoxy resin: solid epoxy resin) are better in terms of mass ratio. It is 1: 0.1 ~ 1: 15, more preferably 1: 0.3 ~ 1: 10, and particularly preferably 1: 0.6 ~ 1: 8. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, generally, when used in the form of a resin sheet, moderate adhesiveness can be obtained. In addition, when generally used in the form of a resin sheet, sufficient flexibility can be obtained, and thus the operability is improved. Furthermore, a hardened | cured material which has sufficient breaking strength is generally obtained.

(D) The weight-average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and more preferably from 400 to 1500, from the viewpoint of significantly obtaining the desired effect of the present invention.

The epoxy equivalent of the (D) epoxy resin is preferably focused on the same range as the epoxy equivalent of the epoxy resin (A) described above.

When the resin composition contains (D) epoxy resin, the amount of (D) epoxy resin is preferably 100 parts by mass or more, and more preferably 200 parts by mass relative to 100 parts by mass of (A) epoxy resin. It is more preferably 500 parts by mass or more, particularly preferably 1,000 parts by mass or less, still more preferably 900 parts by mass or less, and particularly preferably 800 parts by mass or less. When the amount of the (D) epoxy resin is concentrated in the aforementioned range, the desired effect of the present invention can be significantly obtained.

When the resin composition contains (D) epoxy resin, the amount of (D) epoxy resin is when the non-volatile content in the resin composition is 100% by mass, preferably 0.3% by mass or more, and It is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, still more preferably 20% by mass or less, still more preferably 16% by mass or less, and even more preferably 14% by mass or less. When the amount of the (D) epoxy resin is concentrated in the aforementioned range, the mechanical strength and insulation reliability of the cured product of the resin composition can be improved.

[6. (E) Hardening accelerator] As an optional component, the resin composition system may contain (E) a hardening accelerator. By using a hardening accelerator, hardening is accelerated | stimulated when hardening a resin composition.

Examples of the (E) hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, and a metal-based hardening accelerator. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are further Better. The hardening accelerators can be used singly or in combination of two or more kinds.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, ( 4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -Ginseng (dimethylaminomethyl) phenol, 1,8-diazinebicyclo (5,4,0) -undecene and the like. Among them, 4-dimethylaminopyridine and 1,8-diazinebicyclo (5,4,0) -undecene are preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 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-cyano Ethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6- [2'-methylimidazole -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine , 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a] benzimidazole, 1-dodecyl Alkyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidium Morpholine, 2-phenyl imidazole and imidazoline compounds and the adduct of an imidazole compound with an epoxy resin. Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

Commercially available products can be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation; "2E4MZ" manufactured by Shikoku Chemical Co., Ltd .;

Examples of the guanidine-based hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, Dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazinebicyclo [4.4.0] dec-5-ene, 7-methyl- 1,5,7-triazinebicyclo [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 and the like. Among them, dicyandiamine and 1,5,7-triazinebicyclo [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 organocobalt complexes such as cobalt (II) acetopyruvate, cobalt (III) acetopyruvate, and copper (II) acetopyruvate. Organic copper complexes, organic zinc complexes such as zinc (II) acetamidate, organic iron complexes such as iron (III) acetamidate, nickel (II) acetamidopyruvates And other organic nickel complexes, and organic manganese complexes such as manganese (II) ethidium pyruvate 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 (E) a hardening accelerator, the amount of the (E) hardening accelerator is 100% by mass based on 100% by mass of the resin component of the resin composition from the viewpoint that the desired effect of the present invention is significantly obtained, 0.01 mass% to 3 mass% is preferred, 0.03 mass% to 1.5 mass% is even more preferred, and 0.05 mass% to 1 mass% is more preferred.

[7. (F) Arbitrary Additives] Resin composition systems may further include arbitrary additives as optional components in addition to the components described above. Examples of such additives include organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thermoplastic resins; thickeners; antifoaming agents; leveling agents; adhesion Additives; colorants; resin additives such as flame retardants. These additives may be used singly or in combination of two or more kinds at an arbitrary ratio.

Although the above-mentioned resin composition may contain a solvent as needed, a solvent-free resin composition containing no solvent is preferable. Even if it does not contain a solvent like this, the said resin composition containing (A) epoxy resin can become fluid when it shape | molds using a compression molding method, and can achieve the outstanding compression moldability. Therefore, this resin composition system can be used as a solventless resin composition.

[8. Manufacturing method of resin composition] The resin composition system can be manufactured by a method of stirring and preparing the components using a stirring device such as a rotary mixer.

[9. Characteristics of resin composition] The above resin composition is excellent in compression moldability. Therefore, when a resin composition layer is formed on a circuit board or a semiconductor wafer by a compression molding method, the resin composition can be filled in each corner. Therefore, by hardening the resin composition layer, an insulating layer having excellent insulation reliability and a sealing layer having excellent sealing reliability can be obtained. For example, using a compression molding apparatus (mold temperature: 130 ° C, molding pressure: 6MPa, curing time: 10 minutes), the above resin composition is compression-molded onto a 12-inch silicon wafer to form a resin composition having a thickness of 300 μm. Physical layer. In this case, the generation of cracks is generally suppressed, and at the same time, the resin composition can be filled at the end of the wafer.

Further, according to the resin composition described above, a cured product having a low linear thermal expansion coefficient can be obtained. Therefore, by using this resin composition, an insulating layer and a sealing layer having a low linear thermal expansion coefficient can be obtained. (2) For example, the above-mentioned resin composition is used to produce a hardened material for evaluation by the method described in Examples, and the linear thermal expansion coefficient of the hardened material for evaluation is measured. In this case, the obtained linear thermal expansion coefficient is generally 10 ppm / ° C or lower, preferably 9 ppm / ° C or lower, and further preferably 8 ppm / ° C or lower. The lower limit is not particularly limited, but is generally 0 ppm / ° C, preferably 1 ppm / ° C or more.

In addition, according to the resin composition described above, a layer of a cured product capable of suppressing warpage can be obtained. Therefore, by using this resin composition, an insulating layer and a sealing layer capable of suppressing warpage of a circuit board and a semiconductor chip package can be obtained. For example, using the above-mentioned resin composition, a hardened layer of the resin composition was formed on a 12-inch silicon wafer by the method described in the examples to prepare a sample substrate. In this case, when the sample substrate is heated and cooled in the order of 35 ° C, 260 ° C, and 35 ° C, the amount of warpage measured by the method described in the examples can generally be set to less than 2 mm.

Moreover, according to the said resin composition, the hardened | cured material which can exhibit high adhesiveness even if it repeats heating and cooling can be obtained. therefore. By using this resin composition, it is possible to obtain an insulating layer or a sealing layer that is unlikely to cause peeling due to a change in temperature. For example, a resin wafer including a hardened material layer of a resin composition and a silicon wafer embedded in the hardened material layer is produced by the method described in the example. When the resin wafer is subjected to a thermal cycle test by the method described in the examples, the occurrence of delamination at the interface between the silicon wafer and the hardened layer is generally suppressed.

The present inventors presume that the mechanism by which the above-mentioned excellent advantages can be obtained based on the resin composition of the present invention is as follows. However, the technical scope of the present invention is not limited by the mechanism described below. The above-mentioned resin composition contains a low viscosity (A) epoxy resin, and therefore has excellent fluidity during compression molding. Therefore, since the resin composition easily enters into a small gap, excellent compression moldability can be achieved. In addition, the (B) inorganic filler contained in the resin composition has a smaller degree of expansion and contraction due to temperature changes than the resin component. Furthermore, since (A) an epoxy resin is hardened in a resin composition, it can function as a soft and flexible component, and can absorb the volume change by temperature change. Therefore, the linear thermal expansion coefficient of the hardened | cured material of a resin composition can be reduced. In addition, as described above, (B) the degree of expansion and contraction of the inorganic filler material due to temperature changes is small, so even if the temperature changes, the stress caused by the temperature changes can be reduced. Moreover, since (A) epoxy resin can function as a soft and flexible component after hardening of a resin composition, even if stress generate | occur | produces in a hardened | cured material, (A) epoxy resin can absorb this stress. Therefore, since the generation of stress that can cause the warpage can be suppressed, suppression of the warpage is possible. Furthermore, since the resin composition is excellent in fluidity as described above, it is difficult for the residual stress after molding of the resin composition to remain. In addition, even if a stress is generated due to a change in temperature, the stress can be absorbed by the epoxy resin (A) as described above. Therefore, the hardened system of the resin composition suppresses stress concentration. Therefore, even if the hardened material of the resin composition is repeatedly heated and cooled, it is difficult to cause damage due to a change in temperature, so that occurrence of delamination due to resin damage can be suppressed.

Generally, the hardened material-based dielectric tangent of the resin composition is low. Therefore, by using this resin composition, an insulating layer having a low dielectric tangent can be obtained. For example, the hardened material layer of a resin composition is manufactured by the method as described in an Example. The dielectric tangent of the hardened layer measured by the measurement method described in the examples is preferably 0.007 or less, and more preferably 0.006 or less. The lower the lower limit of the value of the dielectric tangent, the better, and it can be set to, for example, 0.001 or more.

The resin composition may be liquid or solid, but it is preferably liquid when molding. For example, the resin composition in a liquid state at normal temperature (for example, 20 ° C) may be molded by a compression molding method at normal temperature without special temperature adjustment, or may be heated to an appropriate temperature by a compression molding method. Of molding. In addition, a solid resin composition at normal temperature is generally changed to a liquid state by adjusting the temperature to a higher temperature (for example, 130 ° C), so it can be adjusted by appropriate temperature such as heating and Compression molding. The resin composition generally can be made liquid at an appropriate temperature even if it does not include a solvent, and can be used, for example, as a liquid sealing material.

[10. Use of resin composition] 密封 Taking advantage of the advantages described above, a hardened product of the resin composition can be used to form a sealing layer and an insulating layer. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or an insulating layer.

For example, the resin composition can be suitably used as a resin composition (resin composition for an insulating layer of a semiconductor chip package) for forming an insulating layer of a semiconductor chip package, and as a circuit board (including a printed wiring board). ) Resin composition of the insulating layer (resin composition for the insulating layer of the circuit board). Further, for example, the aforementioned resin composition system can be suitably used as a resin composition (an insulation layer for forming a conductor layer) for forming a conductor layer (including a redistribution layer) formed on the insulation layer and for forming the insulation layer. Forming resin composition).

In addition, for example, the resin composition system can be suitably used as a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer).

Examples of the semiconductor wafer package which can be suitably used as a sealing layer or an insulating layer formed of a cured product of the resin composition include FC-CSP, MIS-BGA package, ETS-BGA package, and Fan-out WLP ( Wafer Level Package), Fan-in WLP, Fan-out PLP (Panel Level Package), Fan-in PLP.

The resin composition may be used as an underfill material, or may be a material such as MUF (Molding Under Filling) used after connecting a semiconductor wafer to a substrate.

Furthermore, the aforementioned resin composition can be used in a wide range of resin compositions such as resin flakes, prepregs, and other sheet-like laminates, solder resists, die-bonding materials, hole-filling resins, and component-embedding resins. in.

[11. Resin Sheet] The resin sheet of the present invention includes a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed from a resin composition.

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

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Polyesters (hereinafter sometimes referred to as "PEN"), etc .; Polycarbonates (hereinafter sometimes referred to as "PC"); Polymethyl methacrylate (hereinafter sometimes referred to as "PMMA"), etc. Materials; cyclic polyolefins; triethylfluorenyl cellulose (hereinafter sometimes referred to as "TAC"); polyether sulfide (hereinafter sometimes referred to as "PES"); polyetherketone; polyfluorene. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred.

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

The support system may apply a treatment such as a matting treatment, a corona discharge treatment, or an antistatic treatment to the surface bonded to the resin composition layer.

Moreover, as a support system, 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. Examples of the release agent that can be used in the release layer of a support with a release layer include a group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. One or more release agents selected from among them. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by LINTEC Corporation, which are alkyd resin-based release agents. Examples of the support with a release layer include "Lumirror T60" manufactured by Toray; "PUREX" manufactured by Teijin; and "Unipeel" manufactured by Unitika.

The thickness of the support is preferably in a range of 5 μm to 75 μm, and more preferably in a range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably set to the above range.

The resin sheet can be produced by applying a resin composition to a support using a coating device such as a die coater. If necessary, the resin composition may be dissolved in an organic solvent to prepare a resin varnish, and the resin varnish may be applied to produce a resin sheet. By using a solvent, viscosity can be adjusted and coating properties can be improved. When a resin varnish is used, the resin varnish is generally dried after coating to form a resin composition layer.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbidine Acetate solvents such as alcohol acetates; Fibrinolytic agents and carbitol solvents such as butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide and dimethylacetamidine Ammonium solvents such as amines (DMAc) and N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds at any ratio.

The drying system can be performed by a known method such as heating and blowing hot air. The content of the organic solvent in the drying condition-based resin composition layer is generally 10% by mass or less, and preferably 5% by mass or less for drying. It varies depending on the boiling point of the organic solvent in the resin varnish. For example, if a resin varnish containing 30% to 60% by mass of organic solvent is used, it is dried for 3 minutes at 50 ° C to 150 ° C. For 10 minutes, a resin composition layer can be formed.

The resin sheet may include any layer other than the support and the resin composition layer as necessary. For example, a protective film may be provided on the surface of the resin sheet that is not in contact with the support of the resin composition layer (that is, the surface on the opposite side from the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust or the like from being attached to the surface of the resin composition layer. When the resin sheet has a protective film, the protective film is peeled off to become a usable resin sheet. The resin sheet can be rolled into a roll shape for storage.

The resin sheet is suitably used for forming an insulating layer (a resin sheet for insulating a semiconductor wafer package) when the semiconductor wafer package is manufactured. For example, in order to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), a resin sheet can be suitably used. Examples of a package using such a substrate include an FC-CSP, a MIS-BGA package, and an ETS-BGA package.

The resin sheet is preferably used for sealing a semiconductor wafer (resin sheet for sealing a semiconductor wafer). Examples of applicable semiconductor wafer packages include Fan-out WLP, Fan-in WLP, Fan-out PLP, Fan-in PLP, and the like.

The resin sheet is used as a MUF material used for connecting a semiconductor wafer to a substrate.

Furthermore, the resin sheet can be used in other wide applications requiring high insulation reliability. For example, the resin sheet is suitably used for forming an insulating layer of a circuit board such as a printed wiring board.

[12. Circuit board] 电路 The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The circuit board can be manufactured by, for example, a manufacturing method including the following steps (1) and (2). (1) A step of forming a resin composition layer on a substrate. (2) A step of thermally curing the resin composition layer to form an insulating layer.

In step (1), a substrate is prepared. 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. Substrate. The base material may include a metal layer such as a copper foil on the surface as a part of the base material. For example, a substrate having a peelable first metal layer and a second metal layer on the surfaces of both surfaces can be used. When such a substrate is used, a conductor layer that is a wiring layer that can function as a circuit wiring is usually formed on a surface on the side opposite to the first metal layer of the second metal layer. Examples of the base material having such a metal layer include an ultra-thin copper foil "Micro Thin" with a supporting copper foil manufactured by Mitsui Metals Mining Corporation.

A conductive layer may be formed on the surface of one or both surfaces of the substrate. In the following description, a member including a base material and a conductive layer formed on the surface of the base material may be appropriately referred to as a "base material with a wiring layer". Examples of the conductive material included in the conductive layer include a group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. A material selected from one or more metals. As the conductive material, a simple metal or an alloy may be used. Examples of the alloy include an alloy of two or more metals selected from the above-mentioned group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper are used as elemental metals from the viewpoints of versatility, cost, and ease of patterning of conductor layers; and alloys Nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys are preferred. Among these, elemental metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys are further preferred, and elemental metals such as copper are particularly preferred.

The conductor layer system may be patterned in order to function as a wiring layer, for example. At this time, the line width (circuit width) / interval (width between circuits) ratio of the conductor layer is not particularly limited, and is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), and further preferably 10/10 μm or less. It is more preferably 5/5 μm or less, still more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch need not be the same throughout the entire conductor layer. The minimum pitch of the conductor layer can be set to, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

The thickness of the conductive layer varies depending on the design of the circuit substrate, preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm. In addition, when the insulating layer is ground or ground to expose the conductor layer after the formation of the insulating layer, and the interlayer connection of the conductor layers is performed, the conductor layer that performs the interlayer connection is connected to the conductor layer that does not perform the interlayer connection. It is preferable that the thickness is different. Among the conductive layers, the thickness of the thickest conductive layer (conductive pillar) varies depending on the design of the circuit substrate, and is preferably 2 μm or more and 100 μm or less. The thickness of the conductive layer can be adjusted by, for example, forming a pattern to be described later. In addition, the conductor layers connected between the layers may be convex.

The conductor layer can be formed, for example, by a method including the steps of: laminating a dry film (photosensitive resist film) on a substrate; using a photomask and exposing and developing the dry film under specified conditions. A pattern to obtain a patterned dry film; a step of using the developed patterned dry film as a plating mask and forming a conductive layer by a plating method such as electrolytic plating; and a patterned dry film Steps of peeling. As the dry film system, a photosensitive dry film made of a photoresist composition can be used, and for example, a dry film formed of a resin such as a novolac resin, an acrylic resin, or the like can be used. The conditions for laminating the substrate and the dry film can be the same as the conditions for laminating the substrate and the resin sheet described later. The peeling of the dry film can be performed using an alkaline peeling solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns can be removed by etching or the like.

After the substrate is prepared, a resin composition layer is formed on the substrate. When a conductor layer is formed on the surface of a base material, it is preferable to form a resin composition layer by embedding a conductor layer in a resin composition layer.

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a substrate. The resin composition layer is bonded to the substrate by, for example, heating and pressing the resin sheet onto the substrate from the support side, so that the lamination system can be performed. Examples of members that heat-press a resin sheet onto a substrate (hereinafter sometimes referred to as "heat-pressed members") include heated metal plates (SUS mirror plates, etc.), metal rollers (SUS rollers, etc.), and the like. . However, instead of pressing the heating and pressing member directly on the resin sheet, it is better to press the resin sheet so that the resin sheet can sufficiently follow the surface unevenness of the substrate through an elastic material such as heat-resistant rubber. good.

The lamination system of the substrate and the resin sheet can be performed, for example, by a vacuum lamination method. 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 in the range of 0.098 MPa to 1.77 MPa, and more preferably in the range of 0.29 MPa to 1.47 MPa. The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination system is preferably implemented under a reduced pressure of 13 hPa or less.

After lamination, the laminated member can be smoothed by heating and pressing the member under normal pressure (atmospheric pressure), for example, 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 above-mentioned lamination. The lamination and smoothing process can be performed continuously using a vacuum laminator.

The formation of the resin composition layer can be performed by, for example, a compression molding method. The molding conditions can be the same conditions as the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor wafer package described later.

After the resin composition layer is formed on the substrate, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, but the curing temperature is generally in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, and more preferably 170 ℃ ~ 200 ℃), the hardening time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally hardened, the resin composition layer may be heated at a temperature lower than the curing temperature to give a preheating treatment. For example, before the resin composition layer is thermally hardened, the resin composition may be generally formed at a temperature of 50 ° C to 120 ° C (preferably 60 ° C to 110 ° C, and preferably 70 ° C to 100 ° C). The pre-heating of the material layer is usually more than 5 minutes (preferably 5 minutes to 150 minutes, and more preferably 15 minutes to 120 minutes).

In this manner, a circuit board having an insulating layer can be manufactured. The method for manufacturing a circuit board may further include an arbitrary step. For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing a circuit board may include a step of peeling a support of the resin sheet. The support system may be peeled before the thermosetting of the resin composition layer, or may be peeled after the thermosetting of the resin composition layer.

The method for manufacturing a circuit board may include, for example, a step of polishing the surface of the insulating layer after forming the insulating layer. The polishing method is not particularly limited. The surface of the insulating layer can be ground, for example, using a flat grinding disk.

The manufacturing method of a circuit board may include the step (3) of interlayer connection of a conductor layer, for example. In this step (3), a conductor layer (for example, a conductor layer formed on the surface of the substrate) provided on one side of the insulating layer is conducted to the other side of the aforementioned conductor layer. This step (3) may include forming a via hole in the insulating layer, and then forming a conductor layer at an appropriate position on the insulating layer including the position where the via hole is formed to perform interlayer connection. In addition, step (3) may include, for example, grinding or grinding the other side of the insulating layer to expose the conductor layer formed on one side of the insulating layer to perform interlayer connection.

In the case of using a via for interlayer connection, for example, after forming a via with an insulating layer formed on a substrate with a wiring layer, a conductor layer is formed on the side opposite to the substrate of the insulating layer to perform interlayer. connection. Examples of the method of forming the through hole include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferred. This laser irradiation system can be performed using a suitable laser processing machine using an arbitrary light source such as a carbon dioxide gas laser, a YAG laser, an excimer laser, and the like. For example, the support side of the resin sheet is irradiated with laser light and penetrates the support and the insulating layer, thereby forming a through hole that exposes the conductor layer on the surface of the substrate.

The laser irradiation can be performed in accordance with appropriate procedures in accordance with the laser processing machine selected. The shape of the through hole is not particularly limited, but is generally circular or substantially circular. The shape of the through-hole refers to the shape of the outline of the opening when viewed in the extending direction of the through-hole.

After the formation of the through hole, it is preferred to perform a step of removing the slag in the through hole. This step is sometimes referred to as the sizing step. For example, if a conductive layer is formed on the insulating layer by a plating step, a wet-type slag removal treatment may be performed on the through hole. When a conductive layer is formed on the insulating layer by a sputtering step, a dry slag removal step such as a plasma treatment step may be performed. Furthermore, the insulation layer can be subjected to a roughening treatment by a step of removing slag.

In addition, before the conductor layer is formed on the insulating layer, the insulating layer may be roughened. According to this roughening treatment, the surface of the insulating layer including the through hole is generally roughened. As the roughening treatment system, arbitrary roughening treatments of a dry type and a wet type can be performed. Examples of the dry roughening treatment include plasma treatment and the like. Examples of the wet roughening treatment include a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution.

After forming the via hole, a conductor layer is formed on the insulating layer. The conductive layer is formed at the position where the through-hole is formed, so that the newly formed conductive layer and the conductive layer on the surface of the substrate are conducted and connected between layers. Examples of the method for forming the conductive layer include a plating method, a sputtering method, and a vapor deposition method. Among them, a plating method is preferred. In a suitable embodiment, the surface of the insulating layer is plated by an appropriate method such as a semi-additive method or a full-additive method to form a conductive layer having a desired wiring pattern. When the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by an erasing method. The material system of the formed conductor layer may be a simple metal or an alloy. The conductor layer system may have a single-layer structure or a multilayer structure including two or more different types of material layers.

Here, an example of an embodiment in which a conductor layer is formed on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating. At this time, at the same time as the formation of the electrolytic plating layer, the through holes are buried by electrolytic plating to form a filled hole. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by a process such as etching to form a conductive layer having a desired wiring pattern. In the formation of the conductive layer, the dry film used in forming the mask pattern is the same as the dry film.

The conductive layer may include not only linear wiring but also electrode pads (land / pads) capable of mounting external terminals, for example. The conductor layer system may be composed of only an electrode pad.

In addition, the conductive layer is formed after the plating seed layer is formed, and the electrolytic plating layer and the hole are filled without using a mask pattern, and can be formed by patterning after etching.

When interlayer connection is performed by grinding or grinding of an insulating layer, for example, after grinding or grinding the insulating layer formed on a substrate with a wiring layer, the conductive layer formed on the substrate is ground. It is exposed on the side opposite to the base material of the insulating layer. As the method of polishing the insulating layer and the method of grinding, any method capable of exposing the conductive layer on the surface of the substrate can be used. Among them, it is preferable that a layer plane of the insulating layer is obtained by grinding or cutting to obtain a parallel ground surface or ground surface. Examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as polishing, and a planar grinding method using a grinding wheel. In addition, when the interlayer connection is performed by grinding or grinding of the insulating layer, it is the same as the case of using the through hole to perform the interlayer connection. The slag removal step, the roughening step, and the insulation A step of forming a conductor layer on the layer. Moreover, it is not necessary to expose all the conductor layers on the surface of the base material, and it is also possible to expose a part thereof.

The method for manufacturing a circuit substrate may include, for example, step (4) of removing a substrate. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. For example, when using a base material having a first metal layer and a second metal layer that can be peeled off, this step (4) can be performed. Hereinafter, suitable examples will be described. A conductor layer is formed on the surface of the second metal layer of the substrate having the first metal layer and the second metal layer. Further, a resin composition layer is formed on the second metal layer so that the conductor layer is embedded in the resin composition layer, and the resin composition layer is thermally cured to obtain an insulating layer. After that, after the interlayer connection is performed as necessary, a portion other than the second metal layer of the base material is peeled off. In addition, the second metal layer is etched and removed using an etchant such as a copper chloride aqueous solution. This makes it possible to remove the substrate. In this case, the base material may be removed in a state in which the protective layer is used to protect the conductor layer as needed.

In other embodiments, the circuit board may be manufactured using a prepreg. The prepreg system is one in which the resin composition is impregnated into the sheet-like fibrous base material by a method such as a hot melt method or a solvent method. Examples of the sheet-like fibrous substrate include glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric. 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, particularly preferably 600 μm or less, and further preferably 1 μm or more. 1.5 μm or more and 2 μm or more. The thickness of the prepreg can be set in the same range as the resin composition layer in the resin sheet described above. The method for manufacturing a circuit board using such a prepreg is basically the same as when a resin sheet is used.

[13. Semiconductor chip package] The semiconductor chip package system according to the first embodiment of the present invention includes the circuit board described above and a semiconductor wafer mounted on the circuit board. The semiconductor wafer package system can be manufactured by bonding a semiconductor wafer to a circuit substrate.

The joining conditions of the circuit substrate and the semiconductor wafer are arbitrary conditions in which the terminal electrodes of the semiconductor wafer and the circuit wiring of the circuit substrate can be connected in a conductor. For example, the conditions used for flip-chip mounting of a semiconductor wafer can be used. In addition, for example, the semiconductor wafer and the circuit board may be bonded via an insulating adhesive.

An example of the bonding method is a method of pressing a semiconductor wafer onto a circuit board. As the pressing condition, the pressing temperature is usually in the range of 120 ° C to 240 ° C (preferably in the range of 130 ° C to 200 ° C, and more preferably in the range of 140 ° C to 180 ° C), and the pressing time is usually 1 A range of seconds to 60 seconds (preferably 5 seconds to 30 seconds).

In addition, as another example of the bonding method, a method in which a semiconductor wafer is re-soldered onto a circuit board and bonded is mentioned. The reflow conditions can be set in the range of 120 ° C to 300 ° C.

After the semiconductor wafer is bonded to the circuit substrate, the semiconductor wafer can be filled with a molded underfill. As the molding underfill, the above-mentioned resin composition may be used, and the above-mentioned resin sheet may also be used.

A semiconductor wafer package system according to a second embodiment of the present invention includes a semiconductor wafer and a cured product of the resin composition sealing the semiconductor wafer. In such a semiconductor chip package, a hardened body of a resin composition generally functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include a Fan-out WLP.

FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of a semiconductor wafer package according to a second embodiment of the present invention. As the semiconductor wafer package 100 of the Fan-out WLP, as shown in FIG. 1, for example, the semiconductor wafer package 100 includes: a semiconductor wafer 110; a sealing layer 120 formed so as to cover the periphery of the semiconductor wafer 110; The sealing layer 120 is a surface on the opposite side, a redistribution layer 130 as an insulating layer, a redistribution layer 140 as a conductor layer, a solder resist layer 150, and a bump 160.

The manufacturing method of such a semiconductor chip package may include the following steps: (A) a step of laminating a temporary fixing film on a substrate, (B) a step of temporarily fixing a semiconductor wafer to the temporary fixing film, (C) A step of forming a sealing layer on a semiconductor wafer, (D) a step of peeling a base material and a temporary fixing film from the semiconductor wafer, and (E) forming a peeled surface of the base material of the semiconductor wafer and the temporary fixing film as insulation The step of forming a redistribution layer of a layer, (F) a step of forming a redistribution layer as a conductor layer on the redistribution forming layer, and (G) a step of forming a solder resist layer on the redistribution layer. In addition, the method for manufacturing a semiconductor chip package may include: (H) cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to perform individual singulation. Hereinafter, this manufacturing method will be described in detail.

(Step (A)) Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions of the substrate and the temporary fixing film can be the same as the lamination conditions of the substrate and the resin sheet in the method for manufacturing a circuit board.

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 resins such as FR-4 substrates, and glass fiber infiltration. A substrate made of a thermosetting treatment; a substrate made of bismaleimide imine triazine resin, such as BT resin.

The temporary fixing film can be any material that can be peeled from the semiconductor wafer and can temporarily fix the semiconductor wafer. Examples of commercially available products include "REVALPHA" manufactured by Nitto Denko Corporation.

(Step (B)) Step (B) is a step of temporarily fixing a semiconductor wafer to a temporary fixing film. The temporary fixing of the semiconductor wafer can be performed using a device such as a flip chip bonding machine, a die bonding machine, or the like. The layout and number of semiconductor wafers can be appropriately set according to the shape and size of the film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor wafers may be arranged in a matrix of a plurality of rows and a plurality of columns and temporarily fixed.

(Step (C)) Step (C) is a step of forming a sealing layer on a semiconductor wafer. The sealing layer is formed by the hardened | cured material of the said resin composition. The sealing layer is generally formed by a method including a step of forming a resin composition layer on a semiconductor wafer and a step of thermally curing the resin composition layer to form a sealing layer.

Since the excellent compression moldability of the resin composition is utilized, it is preferable that the formation of the resin composition layer is performed by a compression molding method. In the compression molding method, a semiconductor wafer and a resin composition are generally placed in a mold, and pressure is applied to the resin composition in the mold, and heat is applied as needed to form a resin composition layer covering the semiconductor wafer. The specific operation of the compression molding method can be, for example, the following. An upper mold and a lower mold are prepared as a mold for compression molding. The resin composition is applied to a semiconductor wafer that is temporarily fixed to the temporarily fixed film as described above. The semiconductor wafer coated with the resin composition is assembled in a lower mold together with a base material and a temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition to perform compression molding. In addition, the specific operation of the compression molding method can be, for example, the following method. An upper mold and a lower mold are prepared as a mold for compression molding. Put the resin composition in the lower mold. The semiconductor wafer is mounted in an upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped such that the resin composition placed in the lower mold is in contact with the semiconductor wafer mounted on the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions differ depending on the composition of the resin composition, and suitable conditions can be adopted in order to achieve a good seal. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition exhibits excellent compression moldability, preferably 80 ° C or higher, more preferably 100 ° C or higher, particularly preferably 120 ° C or higher, and more preferably It is 200 ° C or lower, more preferably 170 ° C or lower, and particularly preferably 150 ° C or lower. The pressure applied during the molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, still more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, still more preferably 30 minutes or less, and particularly preferably 20 minutes or less. Usually, after the formation of the resin composition layer, the mold is removed. The removal of the mold may be performed before the thermosetting of the resin composition layer, or may be performed after the thermosetting.

The resin composition layer can be formed by laminating a resin sheet and a semiconductor wafer. The resin composition layer on the semiconductor wafer can be formed by heating and pressing the resin composition layer of the resin sheet and the semiconductor wafer, for example. The lamination of the resin sheet and the semiconductor wafer usually uses a semiconductor wafer instead of the substrate, and can be performed in the same manner as the lamination of the resin sheet and the substrate in the method of manufacturing a circuit board.

After the resin composition layer is formed on the semiconductor wafer, the resin composition layer is thermally cured to obtain a sealing layer covering the semiconductor wafer. This makes it possible to seal the semiconductor wafer with the cured product of the resin composition. The thermosetting conditions of the resin composition layer can be the same conditions as the thermosetting conditions of the resin composition layer in the method of manufacturing a circuit board. Further, before the resin composition layer is thermally hardened, the resin composition layer may be heated at a temperature lower than the curing temperature to give a preheating treatment. The processing conditions of this preheating process can be the same conditions as the preheating process in the manufacturing method of a circuit board.

(Step (D)) Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor wafer. The peeling method is preferably a method suitable for the material of the temporary fixing film. As a peeling method, the method of peeling by heating, foaming, or expanding a temporary fixing film is mentioned, for example. In addition, examples of the peeling method include a method in which the temporary fixing film is irradiated with ultraviolet rays through a base material, and the adhesive strength of the temporary fixing film is reduced to perform peeling.

In the method of peeling the temporarily fixed film by heating, foaming, or expanding, the heating conditions are usually performed at 100 ° C to 250 ° C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method for detaching the temporarily fixed film by irradiating ultraviolet rays to perform peeling, the irradiation amount of ultraviolet rays is usually 10 mJ / cm ² to 1000 mJ / cm ² .

(Step (E)) (1) Step (E) is a step of forming a rewiring forming layer as an insulating layer on the peeled side of the substrate of the semiconductor wafer and the temporary fixing film.

As the material of the redistribution layer, any material having insulation properties can be used. Among these, from the viewpoint of ease of manufacturing a semiconductor wafer package, a photosensitive resin and a thermosetting resin are preferred. As the thermosetting resin, the resin composition of the present invention can be used.

After the rewiring formation layer is formed, a via hole may be formed in the rewiring formation layer in order to connect the semiconductor wafer and the rewiring layer between layers.

In the method of forming a through hole when the material of the rewiring formation layer is a photosensitive resin, the surface of the rewiring formation layer is usually irradiated with active energy rays through a mask pattern to rewiring the irradiated portion. The formed layer is light cured. Examples of the active energy rays include ultraviolet rays, visible rays, electron rays, and X-rays. Particularly, ultraviolet rays are preferred. The amount of ultraviolet radiation and the irradiation time can be appropriately set in accordance with the photosensitive resin. Examples of the exposure method include a contact exposure method in which a mask pattern is closely adhered to the redistribution layer to perform exposure, and a mask pattern is not adhered to the redistribution layer to perform exposure using parallel light. Non-contact exposure method.

After the rewiring formation layer is photo-cured, the rewiring formation layer is developed and unexposed portions are removed to form a through hole. The development system can perform either wet development or dry development. Examples of the development method include a dipping method, a kneading method, a spray method, a brushing method, and a shaking dipping method, and the kneading method is suitable from the standpoint of resolution.

Examples of a method for forming a through hole when the material of the rewiring forming layer is a thermosetting resin include laser irradiation, etching, mechanical drilling, and the like. Among them, laser irradiation is preferred. The laser irradiation system can be performed using a suitable laser processing machine using a light source such as a carbon dioxide gas laser, a UV-YAG laser, and an excimer laser.

The shape of the through hole is not particularly limited, but is generally considered to be circular (substantially circular). The diameter of the top port of the through hole is preferably 50 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, more preferably 3 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more. Here, the so-called top port diameter of the through hole refers to the diameter of the opening of the through hole on the surface of the redistribution forming layer.

(Step (F)) Step (F) is a step of forming a redistribution layer as a conductor layer on the redistribution forming layer. The method for forming the redistribution layer on the redistribution forming layer can be the same as the method for forming the conductor layer on the insulating layer in the method for manufacturing a circuit board. Further, steps (E) and (F) are repeated, and a redistribution layer and a redistribution forming layer (additional layer) may be alternately deposited.

(Step (G)) Step (G) is a step of forming a solder resist layer on the redistribution layer. As the material of the solder resist layer, any material having insulation properties can be used. Among these, a photosensitive resin and a thermosetting resin are preferred from the viewpoint of ease of manufacturing a semiconductor wafer package. As the thermosetting resin, the resin composition of the present invention can be used.

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

(Step (H)) The manufacturing method of a semiconductor wafer package may include step (H) in addition to steps (A) to (G). Step (H) is a step of cutting a plurality of semiconductor wafer packages into individual semiconductor wafer packages to perform individual singulation. The method for cutting a semiconductor wafer package into individual semiconductor wafer packages is not particularly limited.

In a semiconductor wafer package according to a third embodiment of the present invention, for example, in the semiconductor wafer package 100 shown in FIG. 1, a hardened product of the resin composition of the present invention is used to form a rewiring forming layer 130 or a resistor. The semiconductor chip package of the solder layer 150.

[14. Semiconductor device] As a semiconductor device on which the above-mentioned semiconductor chip package is mounted, for example, it can be provided in, for example, an electrical product (for example, a computer, a mobile phone, a smartphone, a tablet device, a wearable device, a digital camera, a medical device, etc.). Devices, televisions, etc.) and vehicles (such as motorcycles, automobiles, trams, ships, and airplanes). [Example]

Hereinafter, the present invention will be specifically described by showing examples. However, the present invention is not limited to the following examples. In the following descriptions, "parts" and "%" of quantities are indicated. Unless otherwise specified, they mean "mass parts" and "mass%", respectively. In addition, the operations described below are performed under an environment of normal temperature and pressure unless otherwise specified.

[Method for measuring viscosity of epoxy resin] 中 In the following examples and comparative examples, the viscosity of the epoxy resin was measured using an E-type viscometer ("RE-25U" manufactured by Toki Sangyo Co., 1 ° 34 '× R24 Tapered rotor), measured at 45 ° C and 1 rpm.

[Example 1] A liquid polybutadiene epoxy resin ("JP400" manufactured by Japan Soda Co., Ltd., epoxy equivalent weight 230, number average molecular weight Mn = 3500, viscosity 5.5Pa · s at 45 ° C, glass Transfer temperature -62 ° C) 2 parts, spherical silica (average particle size 3.5 μm) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) , Specific surface area: 3.7 m ² / g) 90 parts, acid anhydride hardener ("HNA-100" manufactured by Nippon Ricoh Chemical Co., Ltd., 179 equivalent), 10 parts, glycidylamine epoxy resin ("EP-3980S" manufactured by ADEKA Corporation) , Epoxy equivalent 115) 3 parts, glycidylamine epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95) 7 parts, bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC Corporation), 3 parts of epoxy equivalents 173) and 0.1 part of imidazole-based hardening accelerator ("2E4MZ" manufactured by Shikoku Chemical Co., Ltd.) were mixed to obtain a resin composition.

[Example 2] 5 parts of a cresol novolac type hardener ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl equivalent 117) was used instead of an acid anhydride hardener ("HNA-100" manufactured by Nippon Physico Chemical Corporation) 10 Serving. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Example 3] 替代 5 parts of a liquid novolac phenol hardener ("MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., 141 phenolic hydroxyl equivalent) was used instead of an acid anhydride hardener ("HNA-100" manufactured by New Japan Physicochemical Corporation) ) 10 servings. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Example 4] The amount of the glycidylamine epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation) was changed from 7 parts to 8 parts. In addition, 2 parts of an aliphatic epoxy resin ("YED-216D" manufactured by Mitsubishi Chemical Corporation, and an epoxy equivalent of 120) were used instead of 3 parts of a bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC). Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Example 5] 替代 5 parts of a liquid novolac phenol hardener ("MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., 141 phenolic hydroxyl equivalent) was used instead of an acid anhydride hardener ("HNA-100" manufactured by New Japan Physicochemical Corporation) ) 10 servings. In addition, 7 parts of a glycidylamine type epoxy resin ("ELM-100H" manufactured by Sumitomo Chemical Co., Ltd., and an epoxy equivalent of 106) were used instead of 7 parts of a glycidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation). Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Comparative Example 1] 2 parts of polybutadiene epoxy resin ("JP-200" manufactured by Soda Co., Ltd., epoxy equivalent 210-240, number average molecular weight Mn = 2200, and viscosity 100Pa · s at 45 ° C) were used in 2 parts, It replaces 2 parts of liquid polybutadiene epoxy resin ("JP400" manufactured by Soda Co., Ltd.). Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Comparative Example 2] 替代 Instead of liquid, 2 parts of polybutadiene epoxy resin ("PB-3600" manufactured by DAICEL, epoxy equivalent 193, number average molecular weight Mn = 5900, and viscosity 45Pa · s at 45 ° C) were used. 2 parts of polybutadiene epoxy resin ("JP400" manufactured by Soda Co., Ltd.). In addition, 5 parts of a cresol novolac-type hardener ("KA-1160" manufactured by DIC Corporation, 117 phenolic hydroxyl equivalent) was used instead of 10 parts of an acid anhydride hardener ("HNA-100" manufactured by Nippon Physico Chemical Corporation). Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Comparative Example 3] Liquid polybutadiene epoxy resin ("JP400" manufactured by Soda Co., Ltd.) was not used. In addition, 5 parts of a cresol novolac type hardener ("KA-1160" manufactured by DIC Corporation, phenolic hydroxyl equivalent 117) was used in place of the acid anhydride hardener ("HNA-100" manufactured by Shinnippon Physico Chemical Corporation, and 179 equivalent anhydride) 10 servings. Furthermore, the amount of the glycidylamine type epoxy resin ("EP-3980S" made by ADEKA Corporation, epoxy equivalent 115) was changed from 3 parts to 5 parts. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin composition.

[Measurement of Linear Thermal Expansion Coefficient (CTE) of a hardened material of a resin composition] (Production of hardened material for evaluation) Preparation of a polyethylene terephthalate film subjected to release treatment on one side ("501010" manufactured by LINTEC Corporation) ", Thickness is 38μm, 240mm square). On the untreated surface of the polyethylene terephthalate film that has not been subjected to release treatment, a glass cloth substrate epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Panasonic Corporation, thickness 0.7) mm, 255 mm square), and four sides were fixed with polyimide and adhesive tape (width 10 mm). Thereby, a fixed PET film including a polyethylene terephthalate film and a glass cloth substrate epoxy resin double-sided copper-clad laminate can be obtained.

Methyl ethyl ketone was added to the resin compositions produced in the examples and comparative examples and diluted, and the viscosity of the resin composition was adjusted to 4000 mPa · s. In addition, as a support, a polyethylene terephthalate film ("Lumirror" manufactured by Toray Co., Ltd.) was subjected to a mold release treatment using an alkyd resin-based release agent ("AL-5" manufactured by LINTEC). R80 ", thickness of 38 µm, softening point of 130 ° C). Using a die coater, the resin composition adjusted in viscosity as described above was applied to the support so that the thickness of the dried resin composition layer became 100 μm. The coated resin composition layer was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin sheet including a support and a resin composition layer.

Each resin sheet (the thickness of the resin composition layer was 100 μm) was cut into a 200 mm square square. Using a batch type vacuum pressure laminating machine (Nikko Materials Co., Ltd.'s two-stage build-up laminating machine "CVP700"), the resin composition layer was fixed to the polyethylene terephthalate film side of the PET film. The laminated resin sheet is laminated in such a manner that the centers of the faces (that is, the faces to which the demoulding treatment is applied) are laminated to obtain a multilayer sample. The lamination system was decompressed for 30 seconds and the air pressure was adjusted to 13 hPa or less, and then the pressure was pressed for 30 seconds at a temperature of 100 ° C and a pressure of 0.74 MPa.

Next, the obtained multilayer sample was put into a baking oven at 100 ° C. and heated for 30 minutes, and then transferred to a baking oven at 175 ° C. and heated for 30 minutes to thermally harden the resin composition layer. After that, the multilayer sample was taken out in a room temperature environment and the support was peeled off, and then put into a baking oven at 190 ° C. and heated for 90 minutes to further heat-harden the resin composition layer. The obtained multi-layered sample comprises a cured product layer hardened by a resin composition layer, a polyethylene terephthalate film, and an epoxy double-sided copper-clad laminate on a glass cloth substrate in this order.

After the aforementioned heat curing, the polyimide and the adhesive tape were peeled off, and the glass cloth substrate epoxy resin double-sided copper-clad laminate was peeled off, and then the polyethylene terephthalate film was peeled off, so that A hardened product of a thin-plate resin composition was obtained. The obtained hardened | cured material may be called "an evaluation hardened | cured material."

(CTE measurement) 前述 The test hardened body was cut into a width of 5 mm and a length of 15 mm to obtain a test piece. For this test piece, a thermomechanical analysis device ("Thermo Plus TMA8310" manufactured by Rigaku Corporation) was used to perform thermomechanical analysis by a tensile load method. Specifically, the test piece was mounted on the thermo-mechanical analysis device, and the measurement was performed twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./minute. Further, in the second measurement, the linear thermal expansion coefficient (ppm / ° C) in the plane direction in a range from 25 ° C to 150 ° C was calculated.

[Measurement of the amount of warpage] The compression molding apparatus (mold temperature: 130 ° C., pressure: 6 MPa, curing time: 10 minutes) was used to compression-mold the resin compositions produced in Examples and Comparative Examples to 12 inches of silicon. On the wafer, a resin composition layer having a thickness of 300 μm was formed. Thereafter, the resin composition layer was thermally cured by heating at 180 ° C for 90 minutes. Thereby, a sample substrate including a silicon wafer and a hardened layer of a resin composition can be obtained.

The amount of warpage when the sample substrate was heated and cooled in the order of 35 ° C, 260 ° C, and 35 ° C was measured using a shading measurement device ("ThermoireAXP" manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24, a specification of the Electronic Information Technology Industry Association. Specifically, the entire data of the substrate surface in the measurement area is calculated as a reference plane by a hypothetical plane calculated by the least square method, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane is determined as the warpage amount . If the warpage amount is less than 2 mm, it is judged as "good", and if it is 2 mm or more, it is judged as "bad".

[Evaluation of Adhesion] A 12-inch silicon wafer was attached to a thermal release tape (Thermal release tape; "REVALPHA" manufactured by Nitto Denko Corporation) having adhesiveness at normal temperature and easily peeling off when heated. On this thermal release sheet, 100 1 cm square silicon wafers (thickness: 400 μm) were placed at regular intervals. Next, using a compression molding apparatus (mold temperature: 130 ° C., pressure: 6 MPa, curing time: 10 minutes), the resin compositions produced in the examples and comparative examples were compression-molded on a thermally peelable sheet on which a silicon wafer was placed. Thus, a resin composition layer having a thickness of 500 μm in which a silicon wafer is embedded is formed. Heating is performed at 180 ° C., and the thermally peelable sheet is in a peelable state, thereby removing the thermally peelable sheet and the silicon wafer. Thereafter, the resin composition layer was heated at 180 ° C. for 90 minutes to thermally harden the resin composition layer. Thereby, a resin wafer including a hardened material layer of a resin composition and a silicon wafer embedded in the hardened material layer can be obtained.

After that, a thermal cycle test of the resin wafer was performed. This thermal cycle test is a test in which cooling to -55 ° C and heating to 125 ° C are performed as one cycle, and the aforementioned cooling and heating are repeated for 1,000 cycles. The resin wafer was observed after the thermal cycle test, and it was judged as "poor" if delamination occurred at the interface between the silicon wafer and the hardened layer, and judged as "good" if delamination did not occur. In addition, if a crack is generated on the surface of the resin composition layer after compression molding of the resin composition, it is determined as "crack".

[Evaluation of Compression Moldability] The compression molding apparatus (mold temperature: 130 ° C, pressure: 6MPa, curing time: 10 minutes) was used to compression-mold the resin compositions produced in the examples and comparative examples to 12 inches of silicon crystals. And a resin composition layer having a thickness of 300 μm was formed on the circle. Then, the resin composition layer is observed, and the resin composition can be judged to be "good" when it is filled in the wafer end portion, and if it is not filled, it is judged to be "bad". After compression molding, the resin composition layer is When a crack occurs on the surface of the surface, it is judged as "crack."

[Measurement method of dielectric tangent] (1) Using a compression molding apparatus (mold temperature: 130 ° C, pressure: 6MPa, curing time: 10 minutes), the resin compositions produced in the examples and comparative examples were compression-molded to the surface and demolded. The treated SUS board was formed into a resin composition layer having a thickness of 300 μm. The SUS plate was peeled off, and the resin composition layer was thermally hardened by heating at 180 ° C. for 90 minutes to obtain a cured product layer of the resin composition. This hardened layer was cut into a length of 80 mm and a width of 2 mm to obtain an evaluation sample for measurement of a dielectric tangent. For this evaluation sample, a cavity resonance perturbation method using an analysis device ("HP8362B" manufactured by Agilent Technologies) was used to measure the medium at a measurement temperature of 23 ° C and a measurement frequency of 5.8 GHz. Electric tangent.

[Results] (1) The results of the above examples and comparative examples are shown in the following table.

[Review] (1) As can be seen from Table 1, the resin composition of the Examples is excellent in compression moldability. Moreover, the hardened | cured material series of the resin composition which concerns on an Example has a low linear thermal expansion coefficient, can suppress a warp, and is excellent in high adhesiveness even by repeated heating and cooling. Accordingly, according to the present invention, it is possible to obtain a resin composition layer having a low linear thermal expansion coefficient, suppressing warpage, and obtaining a hardened product with high adhesion even after repeated heating and cooling, and it is confirmed that excellent compression moldability can be achieved. . In addition, by comparing Comparative Example 3 and Examples which are not used for an epoxy resin having an olefin skeleton in the molecule, it is confirmed that if the resin composition of the present invention is used for an epoxy resin having an olefin skeleton in the molecule, it is generally A hardened product having a lower dielectric tangent can be obtained. In addition, in Examples 1 to 5, even when the components (D) to (E) are not contained, the degree may be different, but it is confirmed that the same results as those of the above examples are summarized.

100‧‧‧ semiconductor chip package

110‧‧‧Semiconductor wafer

120‧‧‧Sealing layer

130‧‧‧ redistribution layer

140‧‧‧ redistribution layer

150‧‧‧solder resist layer

160‧‧‧ bump

[FIG. 1] FIG. 1 is a sectional view schematically showing a Fan-out type WLP as an example of a semiconductor chip package according to a second embodiment of the present invention.

Claims (14)

A resin composition comprising: (A) an epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C. and having an olefin skeleton in the molecule, (B) inorganic filler, and (C) hardener. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure in the molecule. The resin composition according to claim 1, wherein the viscosity of the component (A) at 45 ° C is 15 Pa · s or less. For example, the resin composition of claim 1, wherein the content of the component (A) is 0.2% to 10% by mass relative to 100% by mass of the non-volatile component of the resin composition. The resin composition according to claim 1, wherein the average particle diameter of the component (B) is 0.1 μm to 10 μm. The resin composition according to claim 1, wherein the component (C) is an acid anhydride-based hardener or a phenol-based hardener. The resin composition according to claim 1, further comprising (D) an epoxy resin other than the (A) component. The resin composition according to claim 1, further comprising (E) a hardening accelerator. The resin composition according to claim 1, which is a resin composition for semiconductor sealing or an insulating layer. The resin composition according to claim 1, which is a liquid resin composition. A resin sheet comprising: a support body and a resin composition layer provided on the support body, and the resin composition layer comprising the resin composition of any one of claims 1 to 10. A circuit board including an insulating layer, characterized in that the insulating layer is formed of a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor chip package comprising: (i) the circuit board of claim 12 and (ii) a semiconductor wafer mounted on the aforementioned circuit board. A semiconductor wafer package comprising: (i) a semiconductor wafer and (ii) a hardened resin composition of any one of the claims 1 to 10 for sealing the semiconductor wafer.