JP6816667B2 - Resin composition - Google Patents

Description

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

In recent years, the demand for small high-performance electronic devices such as smartphones and tablet devices has been increasing, and along with this, the insulating layer for semiconductor chip packages used in these small electronic devices is also required to have higher functionality. .. As such an insulating layer, for example, one formed by curing a resin composition is known (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2014-55233 International Publication No. 2014/157446

The insulating layer is required to have a low dielectric loss tangent in order to reduce electrical signal loss. As a result of these studies, the present inventor has found that an insulating layer having a low dielectric loss tangent can be obtained by using a resin composition containing an epoxy resin having an alkene skeleton in the molecule. However, as a result of further studies by the present inventor, it has been found that a resin composition containing an epoxy resin having an alkene skeleton in the molecule has low compression moldability. With a resin composition having low compression moldability, it is difficult to fill every corner of the resin composition when the resin composition layer is to be formed by the compression molding method.

Further, in recent years, a smaller semiconductor chip package has been demanded, and therefore, the insulating layer used for the semiconductor chip package is required to be further thinned. Therefore, it is desired to develop an insulating layer having a low coefficient of linear thermal expansion (CTE, sometimes referred to as a coefficient of thermal expansion) and capable of suppressing warpage. Further, the insulating layer is required to have high adhesion even after repeated heating and cooling. For example, the insulating layer in close contact with the silicon chip is hard to be peeled off from the silicon chip even after repeated heating and cooling. Is required. However, the conventional resin composition containing an epoxy resin having an alkene skeleton in the molecule has not achieved satisfactory performance in the evaluation of the coefficient of linear thermal expansion, warpage and adhesion.

The resin composition used for forming the insulating layer may be used as a sealing material for a semiconductor chip package. For example, it is conceivable to use a cured product obtained by curing a resin composition as a sealing layer for sealing a semiconductor chip in a semiconductor chip package. The above-mentioned problems also occur when the resin composition is used as a sealing material for a semiconductor chip package.

The present invention has been devised in view of the above problems, and can obtain a cured product having a low coefficient of linear thermal expansion, capable of suppressing warpage, and having high adhesion even after repeated heating and cooling. , A resin composition having excellent compressibility; a resin sheet having a resin composition layer containing the above resin composition; a circuit board including an insulating layer formed by a cured product of the above resin composition; and the above resin. It is an object of the present invention to provide a semiconductor chip package containing a cured product of a composition.

As a result of diligent studies to solve the above problems, the present inventor has found that (A) an epoxy resin having a viscosity in a predetermined range at 45 ° C. and having an alken skeleton in the molecule, (B) an inorganic filler. The present invention has been completed by finding that the above-mentioned problems can be solved by a resin composition containing (C) a curing agent in combination.
That is, the present invention includes the following.

[1] (A) An epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C. and an alkene skeleton in the molecule.
A resin composition containing (B) an inorganic filler and (C) a curing agent.
[2] The resin composition according to [1], wherein the component (A) has a polybutadiene structure in the molecule.
[3] The resin composition according to [1] or [2], wherein the component (A) has a viscosity of 15 Pa · s or less at 45 ° C.
[4] In any one of [1] to [3], the content of the component (A) is 0.2% by mass to 10% by mass with respect to 100% by mass of the non-volatile component of the resin composition. The resin composition described.
[5] The resin composition according to any one of [1] to [4], wherein the average particle size 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 curing agent or a phenol-based curing agent.
[7] The resin composition according to any one of [1] to [6], further containing (D) an epoxy resin other than the component (A).
[8] The resin composition according to any one of [1] to [7], further comprising (E) a curing accelerator.
[9] The resin composition according to any one of [1] to [8], which is a resin composition for encapsulating a semiconductor 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 having a support and a resin composition layer containing the resin composition according to any one of [1] to [10] provided on the support.
[12] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10].
[13] A semiconductor chip package including the circuit board according to [12] and a semiconductor chip mounted on the circuit board.
[14] A semiconductor chip package containing a semiconductor chip and a cured product of the resin composition according to any one of [1] to [10] that seals the semiconductor chip.

According to the present invention, a resin composition having a low coefficient of linear thermal expansion, being able to suppress warpage, being able to obtain a cured product having high adhesion even after repeated heating and cooling, and having excellent compression moldability; A resin sheet having a resin composition layer containing the resin composition; a circuit board containing an insulating layer formed by a cured product of the resin composition; and a semiconductor chip package containing the cured product of the resin composition. Can be provided.

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

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

In the following description, the "resin component" of the resin composition refers to a non-volatile component contained in the resin composition excluding the inorganic filler.

[1. Outline of resin composition]
The resin composition of the present invention comprises (A) an epoxy resin having a viscosity in a predetermined range at 45 ° C. and having an alkene skeleton in the molecule, (B) an inorganic filler, and (C) a curing agent. Including. In the following description, the "epoxy resin having a viscosity in a predetermined range at 45 ° C. and having an alkene skeleton in the molecule" as the component (A) may be referred to as "(A) epoxy resin".

By containing the above-mentioned components (A), (B) and (C) in combination, the resin composition is excellent in compression moldability, has a low coefficient of linear thermal expansion, can suppress warpage, and is heated and It is possible to obtain the desired effect of the present invention that a cured product capable of exhibiting high adhesion can be obtained even after repeated cooling. The cured product of this resin composition can be preferably used as an insulating layer and a sealing material for a semiconductor chip package by taking advantage of its excellent properties.

Further, the resin composition may further contain an arbitrary component in combination with the component (A), the component (B) and the component (C). Examples of the optional component include (D) epoxy resin other than (A) epoxy resin, (E) curing accelerator, and the like.

[2. (A) Epoxy resin]
The epoxy resin (A) has a viscosity in a predetermined range at 45 ° C. The specific viscosity of the epoxy resin (A) at 45 ° C. is usually 20 Pa · s or less, preferably 15 Pa · s or less, more preferably 10 Pa · s or less, and particularly preferably 6.0 Pa · s or less. By using the epoxy resin (A) having such a viscosity, the compression moldability of the resin composition can be improved. Further, by using the epoxy resin (A) having such a viscosity, it is possible to obtain a cured product having a low coefficient of linear thermal expansion, suppressing warpage, and exhibiting high adhesion even after repeated heating and cooling. it can. The lower limit of the viscosity of the epoxy resin at 45 ° C. is not particularly limited, but may be, for example, 1 Pa · s or more, 2 Pa · s or more, 3 Pa · s or more.

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

Further, the epoxy resin (A) has an alkene skeleton in the molecule. Here, the alkene skeleton indicates a structure represented by the following formula (1). There is no limitation on the atom to which the carbon atom bond represented by the formula (1) is bonded, but it is usually a hydrogen atom or a carbon atom. By using the epoxy resin (A) having an alkene skeleton in this way, the dielectric loss tangent of the cured product of the resin composition can usually be lowered. Furthermore, it is usually possible to improve the insulating property of the cured product and lower the hygroscopicity.

(A) The epoxy resin may have an alkene skeleton in the main chain of the molecule, may have an alkene skeleton in the side chain of the molecule, and may have an alkene skeleton in both the main chain and the side chain of the molecule. It may have an alkene skeleton. Above all, it is preferable to have an alkene skeleton in the side chain of the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product.

The epoxy resin (A) having an alkene skeleton usually contains a structural unit having an alkene skeleton in its molecule. As this structural unit, a divalent hydrocarbon group having an alkene skeleton is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric tangent of the cured product, and the alkene skeleton is used. A divalent aliphatic hydrocarbon group having a alkene skeleton is more preferable, and a divalent chain aliphatic hydrocarbon group having an alkene skeleton is particularly preferable.

The number of carbon atoms of the structural unit having an alkene skeleton is preferably 2 or more, more preferably 2 or more, from the viewpoint of significantly obtaining the desired effect of the present invention and effectively reducing the dielectric loss tangent of the cured product. It is 3 or more, particularly preferably 4 or more, preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.

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

Preferred examples of the structural unit having an alkene skeleton include the structural unit represented by the following formula (2) or formula (3). Both the structural unit represented by the formula (2) and the structural unit represented by the 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 these, the structural unit represented by the formula (2) is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product.

(A) The number of the structural units having an alkene skeleton contained in the epoxy resin molecule may be one or two or more. From the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product, the (A) epoxy resin has the above-mentioned structural unit having an alkene skeleton as a repeating unit in the molecule. It is preferable to include two or more.

In particular, the epoxy resin (A) preferably has a polybutadiene structure in the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product. The polybutadiene structure refers to a structure that can be formed by polymerizing butadiene. Specific examples of the polybutadiene structure include a structure containing 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. Above all, the epoxy resin (A) preferably contains two or more structural units represented by the formula (2) in one molecule.

Furthermore, it is preferable that the number of structural units represented by the formula (2) per molecule of the epoxy resin (A) is larger than the number of structural units represented by the formula (3). As a result, the desired effect of the present invention can be remarkably obtained, in particular, the compression moldability of the resin composition can be effectively enhanced, and the adhesion of the cured product when heating and cooling are repeated. Can be effectively enhanced.

In addition, the epoxy resin (A) usually has an epoxy group. (A) The epoxy resin may have an epoxy group in the main chain of the molecule, may have an epoxy group in the side chain of the molecule, and may have an epoxy group in both the main chain and the side chain of the molecule. It may have an epoxy group. Above all, it is preferable to have an epoxy group in the side chain of the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product.

The epoxy resin (A) may have an epoxy group in the structural unit having an alkene skeleton, but from the viewpoint of remarkably obtaining the desired effect of the present invention and effectively lowering the dielectric loss tangent of the cured product. From the viewpoint of the above, it is preferable to have an epoxy group in a structural unit different from the above-mentioned structural unit having an alkene skeleton.

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

Preferred examples of the structural unit having an epoxy skeleton include a structural unit represented by the following formula (4) or formula (5). The structural unit represented by the formula (4) can be formed, for example, by epoxidizing polybutadiene containing the structural unit represented by the formula (2). Further, the structural unit represented by the formula (5) can be formed, for example, by epoxidizing polybutadiene containing the structural unit represented by the formula (3). Among these, the structural unit represented by the formula (4) is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product.

Furthermore, it is preferable that the number of structural units represented by the formula (4) per molecule of the epoxy resin (A) is larger than the number of structural units represented by the formula (5). As a result, the desired effect of the present invention can be remarkably obtained, in particular, the compression moldability of the resin composition can be effectively enhanced, and the adhesion of the cured product when heating and cooling are repeated. Can be effectively enhanced.

The epoxy resin (A) preferably has two or more epoxy groups in the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention. Further, the epoxy resin (A) is preferably an aliphatic epoxy resin that does not contain an aromatic ring in the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention.

Examples of the molecular structure of the epoxy resin (A) include those represented by the formula (6). In equation (6), m and n each independently represent a natural number.

Specific examples of the epoxy resin (A) include "JP400" manufactured by Nippon Soda Corporation, which has a molecular structure represented by the above formula (6). Further, as the component (A), one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

In general, the epoxy resin may be a liquid epoxy resin at a temperature of 20 ° C. (hereinafter sometimes referred to as "liquid epoxy resin") or a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as "solid epoxy resin"). ) And can be classified. The epoxy resin (A) may be a solid epoxy resin, but is preferably a liquid epoxy resin. Since the epoxy resin (A) is a liquid epoxy resin, the compression moldability of the resin composition can be effectively enhanced, and the adhesion of the cured product when heating and cooling are repeated is effectively enhanced. be able to.

The number average molecular weight Mn of the epoxy resin (A) is preferably 2500 or more, more preferably 3000 or more, particularly preferably 3200 or more, preferably 5500 or less, more preferably 5000 or less, and particularly preferably 4000 or less. (A) When the number average molecular weight Mn of the epoxy resin is at least the lower limit of the above range, the compression moldability of the resin composition is particularly improved, and the linear thermal expansion coefficient of the cured product of the resin composition is effectively improved. It can be lowered, the ability of the cured product to suppress warpage can be effectively increased, and the peeling of the cured product due to heating and cooling can be effectively suppressed. Further, when the number average molecular weight Mn of the epoxy resin (A) is not more than the upper limit of the above range, the compression moldability of the resin composition is particularly improved, and the linear thermal expansion coefficient of the cured product of the resin composition is effective. The toughness of the cured product of the resin composition can be increased to effectively suppress the occurrence of cracks.

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

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. When the epoxy equivalent of the epoxy resin (A) is in the above range, the crosslink density of the cured product of the resin composition is increased, and an insulating layer having a small surface roughness can be obtained. Epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group. Epoxy equivalents can be measured according to JIS K7236.

The glass transition temperature of the epoxy resin (A) is preferably −20 ° C. or lower, more preferably −30 ° C. or lower, particularly preferably −40 ° C. or lower, preferably −90 ° C. or higher, and more preferably −80 ° C. or higher. , Especially preferably −70 ° C. or higher. When the epoxy resin (A) has a glass transition temperature in the above range, the desired effect of the present invention can be remarkably obtained.

The amount of the epoxy resin (A) in the resin composition is preferably 0.2% by mass or more, based on 100% by mass of the non-volatile component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. It is preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, preferably 10% by mass or less, more preferably 9.5% by mass or less, and particularly preferably 9% by mass or less. Further, usually, by keeping the amount of the epoxy resin (A) within the above range, the dielectric loss tangent of the cured product of the resin composition can be lowered.

[3. (B) Inorganic filler]
The resin composition contains an inorganic filler as the component (B). 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.

(B) An inorganic compound is used as the material of the inorganic filler. Examples of the material of the inorganic filler (B) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. (B) As the inorganic filler, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Usually, (B) the inorganic filler is contained in the resin composition in the form 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, more preferably 8.0 μm or less. Particularly preferably, it is 5.0 μm or less. (B) When the average particle size of the inorganic filler is within the above range, the desired effect of the present invention can be remarkably obtained. In particular, when the average particle size of the inorganic filler (B) is not more than the upper limit of the above range, the compression moldability of the resin composition can be effectively enhanced and the flow mark can be reduced. In addition, the adhesion of the cured product when heating and cooling are repeated can be effectively enhanced. Further, since the average particle size of the inorganic filler (B) is within the above range, the surface roughness of the insulating layer can be lowered when the insulating layer is usually formed of a cured product of the resin composition.

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

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

The inorganic filler (B) is preferably surface-treated with an appropriate surface treatment agent. By surface treatment, (B) the moisture resistance and dispersibility of the inorganic filler can be enhanced. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates. Examples include system coupling agents.

Examples of commercially available surface treatment agents include "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBM5783" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-aminooctylrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (Phenyltrimethoxysilane), "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane coupling agent) and the like can be mentioned. Among them, a nitrogen atom-containing silane coupling agent is preferable, a phenyl group-containing aminosilane-based coupling agent is more preferable, N-phenyl-3-aminoalkyltrimethoxysilane is more preferable, and N-phenyl-3-aminopropyl is more preferable. More preferred are trimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane. Further, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of (B) the inorganic filler. (B) carbon content per unit surface area of the inorganic filler, (B) from the viewpoint of the dispersibility of the inorganic filler improved, preferably 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, Particularly preferably, it 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 sheet form, the amount of carbon is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, particularly preferably. Is 0.5 mg / m ² or less.

The amount of carbon per unit surface area of the (B) inorganic filler is determined after the surface-treated (B) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter, may be abbreviated as “MEK”)). , Can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (B) inorganic filler surface-treated with a surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the (B) inorganic filler can be measured using a carbon analyzer. As the 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, still more preferably 70% by mass, based on 100% by mass of the non-volatile component in the resin composition. It is more than 95% by mass, more preferably 90% by mass or less, still more preferably 86% by mass or less. When the amount of the inorganic filler (B) is in the above range, the desired effect of the present invention can be remarkably obtained, and in particular, the coefficient of linear thermal expansion of the resin composition can be effectively lowered.

[4. (C) Hardener]
The resin composition contains a curing agent as the component (C). The curing agent (C) usually has a function of reacting with an epoxy resin such as (A) epoxy resin and (D) epoxy resin to cure the resin composition. (C) As the curing agent, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

As the curing agent (C), a compound capable of reacting with an epoxy resin to cure the resin composition can be used. For example, an acid anhydride-based curing agent, a phenol-based curing agent, an active ester-based curing agent, etc. Examples thereof include cyanate ester-based curing agents, benzoxazine-based curing agents, and carbodiimide-based curing agents. Among them, an acid anhydride-based curing agent and a phenol-based curing agent are preferable from the viewpoint of remarkably obtaining the effect 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 curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and methylnadic hydride. Anhydride, trialkyltetrahydrophthalic anhydride, succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trihydride Merit acid, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'- Diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2-C] furan-1 , 3-Dione, ethylene glycol bis (anhydrotrimeritate), polymer-type acid anhydrides such as styrene / maleic acid resin in which styrene and maleic acid are copolymerized, and the like.

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

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

Examples of the active ester-based curing agent include curing agents having one or more active ester groups in one molecule. Among them, as the active ester-based curing agent, two or more ester groups having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are contained in one molecule. The compound having is preferable. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. ..

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Preferred specific examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. Examples include active ester compounds containing. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester-based curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", and "" HPC-8000-65T "," HPC-8000H-65TM "," EXB-8000L "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC); as an active ester compound containing a naphthalene structure. "EXB9416-70BK" (manufactured by DIC); "DC808" as an active ester compound containing an acetylated product of phenol novolac (manufactured by Mitsubishi Chemical Co., Ltd.); ); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent that is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent that is a benzoyl compound of phenol novolac. "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.); and the like.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Examples thereof include polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and the like; prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Ronza Japan Co., Ltd .; "ULL-950S" (polyfunctional cyanate ester resin); BA230 ”,“ BA230S75 ”(prepolymer in which part or all of bisphenol A disyanate is triazined to form a trimer); and the like.

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

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

The content of the component (C) is preferably 1% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the resin component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. It is more preferably 10% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less.

When the number of epoxy groups of the epoxy resin (A) and the epoxy resin containing the (D) epoxy resin is 1, the number of active groups of the (C) curing agent is preferably 0.1 or more, more preferably 0.2 or more, and further. It is preferably 0.3 or more, preferably 2 or less, more preferably 1.8 or less, still more preferably 1.6 or less, and particularly preferably 1.4 or less. Here, the "number of epoxy groups of the epoxy resin" is a total value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. The "(C) number of active groups of the curing agent" is a total value obtained by dividing the mass of the non-volatile component of the (C) curing agent present in the resin composition by the active group equivalent. When the number of active groups of the (C) curing agent is in the above range when the number of epoxy groups of the epoxy resin is 1, the desired effect of the present invention can be remarkably obtained, and more usually, the resin composition layer The heat resistance of the cured product is further improved.

[5. (D) Any epoxy resin]
The resin composition may contain (D) an epoxy resin other than the above-mentioned (A) epoxy resin as an arbitrary component.
Examples of the (D) epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy 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 having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexane Examples thereof include a dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The resin composition preferably contains, as the (D) epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass with respect to 100% by mass of the non-volatile component of the epoxy resin (D). % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

As the epoxy resin (D), a liquid epoxy resin may be used, a solid epoxy resin may be used, or a liquid epoxy resin and a solid epoxy resin may be used in combination. Above all, 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.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, an aliphatic epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin, a glycidylamine type epoxy resin, and an aliphatic epoxy resin are preferable. Is more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "EXA-850CRP" (bisphenol A type epoxy resin) manufactured by DIC; Mitsubishi Chemical. "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER152" (phenol novolac type epoxy resin); "630", "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YED-216D" (aliphatic epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin) ); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd .; "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Co., Ltd .; "PB-3600" manufactured by Daicel Co., Ltd. (Epoxy resin having a butadiene structure); "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "ELM-100H" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd .; and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include bixilenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, and biphenyl. Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and bixilenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF A type epoxy resin and a naphthylene ether type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; DIC. "N-690" (cresol novolac type epoxy resin); DIC "N-695" (cresol novolac type epoxy resin); DIC "HP-7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (HP6000) manufactured by DIC. Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayakusha; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayakusha; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation; "ESN485" (naphthol novolac) manufactured by Nippon Steel & Sumitomo Metal Corporation Type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd .; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd .; "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (Fluorene type epoxy resin); "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation and the like can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(D) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is a mass ratio, preferably 1: 0.1 to 1. : 15, more preferably 1: 0.3 to 1:10, particularly preferably 1: 0.6 to 1: 8. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is in such a range, an appropriate adhesiveness is usually provided when used in the form of a resin sheet. In addition, when used in the form of a resin sheet, sufficient flexibility is usually obtained and handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

The weight average molecular weight of the epoxy resin (D) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 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 within the same range as described as the range of the epoxy equivalent of the (A) epoxy resin.

When the resin composition contains (D) epoxy resin, the amount of (D) epoxy resin is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, particularly with respect to 100 parts by mass of (A) epoxy resin. It is preferably 500 parts by mass or more, preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, and particularly preferably 800 parts by mass or less. By keeping the amount of the epoxy resin (D) within the above range, the desired effect of the present invention can be remarkably obtained.

When the resin composition contains (D) epoxy resin, the amount of (D) epoxy resin is preferably 0.3% by mass or more, more preferably 0 when the non-volatile component in the resin composition is 100% by mass. It is 5.5% by mass or more, more preferably 0.7% by mass or more, and preferably 20% by mass or less, more preferably 16% by mass or less, still more preferably 14% by mass or less. By keeping the amount of the epoxy resin (D) within the above range, the mechanical strength and insulation reliability of the cured product of the resin composition can be enhanced.

[6. (E) Curing accelerator]
The resin composition may contain (E) a curing accelerator as an arbitrary component. By using a curing accelerator, curing can be accelerated when the resin composition is cured.

Examples of the (E) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-. Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2,4-diamino-6 -[2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')] -ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')] -Ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, imidazole compounds and epoxy resins Adduct body can be mentioned. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation; "2E4MZ" manufactured by Shikoku Chemicals Corporation; and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned. Of these, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

When the resin composition contains (E) a curing accelerator, the amount of the (E) curing accelerator is based on 100% by mass of the resin component of the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. It is preferably 0.01% by mass to 3% by mass, more preferably 0.03% by mass to 1.5% by mass, and even more preferably 0.05% by mass to 1% by mass.

[7. (F) Any additive]
The resin composition may further contain an arbitrary additive as an arbitrary component in addition to the above-mentioned components. Examples of such additives include organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thermoplastic resins; thickeners; defoaming agents; leveling agents; adhesion-imparting agents. Resin additives such as colorants; flame retardants; etc. may be mentioned. One of these additives may be used alone, or two or more of these additives may be used in combination at any ratio.

The above-mentioned resin composition may contain a solvent, if necessary, but is preferably a solvent-free resin composition containing no solvent. Even if the solvent is not contained in this way, the resin composition containing the epoxy resin (A) can be fluidized when molded by the compression molding method, and excellent compression moldability can be realized. .. Therefore, this resin composition can be used as a solvent-free resin composition.

[8. Method for manufacturing resin composition]
The resin composition can be produced, for example, by a method of stirring the compounding components using a stirring device such as a rotary mixer.

[9. Characteristics of resin composition]
The resin composition described above is excellent in compression moldability. Therefore, when the resin composition layer is formed on the circuit board or the semiconductor chip by the compression molding method, the resin composition can be filled in every corner. Therefore, by curing the resin composition layer, it is possible to obtain an insulating layer having excellent insulation reliability and a sealing layer having excellent sealing reliability.
For example, the above-mentioned resin composition is compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., mold pressure: 6 MPa, cure time: 10 minutes) to a thickness of 300 μm. A resin composition layer is formed. In this case, usually, the resin composition can be filled up to the end of the wafer while suppressing the occurrence of cracks.

Further, according to the resin composition described above, a cured product having a low coefficient of linear thermal expansion can be obtained. Therefore, by using this resin composition, an insulating layer and a sealing layer having a low coefficient of linear thermal expansion can be obtained.
For example, using the resin composition described above, a cured product for evaluation is produced by the method described in Examples, and the coefficient of linear thermal expansion of the cured product for evaluation is measured. In this case, the obtained coefficient of linear thermal expansion is usually 10 ppm / ° C. or lower, preferably 9 ppm / ° C. or lower, and more preferably 8 ppm / ° C. or lower. There is no particular limitation on the lower limit, and it is usually 0 ppm / ° C., preferably 1 ppm / ° C. or higher.

Further, according to the resin composition described above, it is possible to obtain a layer of a cured product capable of suppressing warpage. Therefore, by using this resin composition, it is possible to obtain an insulating layer and a sealing layer capable of suppressing warpage of the circuit board and the semiconductor chip package.
For example, using the resin composition described above, a cured product layer of the resin composition is formed on a 12-inch silicon wafer by the method described in 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 Examples can be usually less than 2 mm.

Further, according to the resin composition described above, it is possible to obtain a cured product capable of exhibiting high adhesion even after repeated heating and cooling. Therefore, by using this resin composition, it is possible to obtain an insulating layer or a sealing layer that is unlikely to peel off due to a temperature change.
For example, a resin wafer including a cured product layer of the resin composition and a silicon chip embedded in the cured product layer is produced by the method described in Examples. When the thermal cycle test is carried out on this resin wafer by the method described in the examples, it is usually possible to suppress the occurrence of delamination at the interface between the silicon chip and the cured product layer.

The present inventor speculates the mechanism by which the resin composition of the present invention provides the above-mentioned excellent advantages as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
Since the resin composition described above contains the low-viscosity (A) epoxy resin, it has excellent fluidity during compression molding. Therefore, the resin composition can easily enter even a small gap, and excellent compression moldability is achieved.
Further, the inorganic filler (B) contained in the resin composition has a smaller degree of expansion and contraction due to temperature change than the resin component. Further, since the epoxy resin (A) can function as a flexible flexible component after curing of the resin composition, it can absorb the volume change due to the temperature change. Therefore, the coefficient of linear thermal expansion of the cured product of the resin composition can be lowered.
Further, as described above, since the (B) inorganic filler has a small degree of expansion and contraction due to a temperature change, even if a temperature change occurs, the stress generated by the temperature change can be reduced. Further, since the epoxy resin (A) can function as a flexible flexible component after the resin composition is cured, even if stress is generated in the cured product, the stress can be absorbed by the epoxy resin (A). Therefore, since the generation of stress that can cause warping can be suppressed, warping can be suppressed.
Further, since the resin composition is excellent in fluidity as described above, residual stress after molding of the resin composition is unlikely to remain. Further, even if stress is generated due to a temperature change, the epoxy resin (A) can absorb the stress as described above. Therefore, stress concentration is suppressed in the cured product of the resin composition. Therefore, even if heating and cooling are repeated, the cured product of the resin composition is less likely to be destroyed by the temperature change, so that the occurrence of delamination due to the resin destruction can be suppressed.

Generally, the cured product of the above resin composition has a low dielectric loss tangent. Therefore, by using this resin composition, an insulating layer having a low dielectric loss tangent can be obtained.
For example, a cured product layer of the resin composition is produced by the method described in Examples. The dielectric loss tangent of this cured product layer measured by the measuring method described in Examples is preferably 0.007 or less, more preferably 0.006 or less. The lower limit of the value of the dielectric loss tangent is preferably as low as possible, for example, 0.001 or more.

The resin composition may be liquid or solid, but it is preferably liquid at the time of molding. For example, a resin composition that is liquid at room temperature (for example, 20 ° C.) may be molded by a compression molding method at room temperature without any special temperature adjustment, or may be molded by a compression molding method by heating to an appropriate temperature. May be done. Further, since a resin composition that is solid at room temperature can usually be liquefied by adjusting the temperature to a higher temperature (for example, 130 ° C.), it can be molded by a compression molding method by appropriately adjusting the temperature such as heating. It is possible. The resin composition can usually be liquefied at an appropriate temperature without containing a solvent, and can be used as, for example, a liquid encapsulant.

[10. Uses of resin composition]
Taking advantage of the above-mentioned advantages, the sealing layer and the insulating layer can be formed by the cured product of the resin composition. Therefore, this resin composition can be used as a resin composition for semiconductor encapsulation or an insulating layer.

For example, the above-mentioned resin composition is a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board). It can be suitably used as a resin composition for forming an insulating layer (a resin composition for an insulating layer of a circuit board).

Further, for example, the above resin composition can be suitably used as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip).

Examples of the semiconductor chip package to which the sealing layer or the insulating layer formed of the cured product of the resin composition can be applied include FC-CSP, MIS-BGA package, ETS-BGA package, and Fan-out type WLP (Wafer). Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, and the like.

Further, the resin composition may be used as an underfill material, or may be used as a material for MUF (Molding Under Filling) used after connecting a semiconductor chip to a substrate, for example.

Further, the resin composition can be used in a wide range of applications in which the resin composition is used, such as a sheet-like laminated material such as a resin sheet and a prepreg, a solder resist, a die bonding material, a hole filling resin, and a component filling resin.

[11. Resin sheet]
The resin sheet of the present invention has 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 of the 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, still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more, 5 μm or more, 10 μm or more, and the like.

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

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyethylene such as (.); Polyethylene (hereinafter sometimes abbreviated as "PC"); Acrylic polymer such as polymethylmethacrylate (hereinafter sometimes abbreviated as "PMMA"); Cyclic polyolefin; Triacetylcellulose (hereinafter referred to as "PMMA"). It may be abbreviated as "TAC"); polyether sulfide (hereinafter, may be abbreviated as "PES"); polyether ketone; polyimide; and the like. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The surface of the support to be joined to the resin composition layer may be subjected to a treatment such as a mat treatment, a corona treatment, or an antistatic treatment.

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

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

The resin sheet can be produced, for example, by applying a resin composition onto a support using a coating device such as a die coater. Further, 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, the viscosity can be adjusted and the coatability can be improved. When a resin varnish is used, the resin varnish is usually dried after application to form a resin composition layer.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitol such as cellosolve and butyl carbitol. Solvents; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. The organic solvent may be used alone or in combination of two or more at any ratio.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

The resin sheet may include any layer other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film similar to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent dust and the like from adhering to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film. Further, the resin sheet can be rolled up and stored.

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

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (resin sheet for encapsulating a semiconductor chip). Applicable semiconductor chip packages include, for example, Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP and the like.

Further, the resin sheet may be used as a material for the MUF used after connecting the semiconductor chip to the substrate.

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

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

In step (1), a base material is prepared. Examples of the substrate include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Further, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a base material having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a base material is used, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on a surface of the second metal layer opposite to the first metal layer. Examples of the base material having such a metal layer include an ultrathin copper foil "Micro Tin" with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

Further, a conductor layer may be formed on one or both surfaces of the base material. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as a “base material with a wiring layer”. As the conductor material contained in the conductor layer, for example, one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Materials containing the above metals can be mentioned. As the conductor material, a single metal may be used, or an alloy may be used. Examples of the alloy include alloys of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chromium alloy as an alloy from the viewpoint of versatility, cost, and ease of patterning of the conductor layer formation. , Copper / nickel alloy, copper / titanium alloy; is preferable. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal; and nickel-chromium alloy; are more preferable, and copper single metal is particularly preferable.

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

The thickness of the conductor layer depends on the design of the circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm. Further, when the insulating layer is polished or ground after the insulating layer is formed to expose the conductor layer and the conductor layer is interconnected, the thickness of the conductor layer to be interconnected and the conductor layer not to be interconnected are thick. Is preferably different. The thickness of the thickest conductor layer (conductive pillar) among the conductor layers depends on the design of the circuit board, but is preferably 2 μm or more and 100 μm or less. The thickness of the conductor layer can be adjusted, for example, by repeating the pattern formation described later. Further, the conductor layer connected between layers may be convex.

The conductor layer is, for example, a step of laminating a dry film (photosensitive resist film) on a base material, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern, and pattern drying. It can be formed by a method including a step of obtaining a film, a step of forming a conductor layer by a plating method such as an electrolytic plating method using the developed pattern dry film as a plating mask, and a step of peeling off the pattern dry film. As the dry film, 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 novolak resin or an acrylic resin can be used. The laminating conditions of the base material and the dry film may be the same as the laminating conditions of the base material and the resin sheet described later. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns may be removed by etching or the like.

After preparing the base material, a resin composition layer is formed on the base material. When the conductor layer is formed on the surface of the base material, it is preferable that the resin composition layer is formed so that the conductor layer is embedded in the resin composition layer.

The formation of the resin composition layer is performed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by attaching the resin composition layer to the base material by heat-pressing the resin sheet to the base material from the support side. Examples of the member for heat-pressing the resin sheet to the base material (hereinafter, may be referred to as “heat-bonding member”) include a heated metal plate (SUS end plate and the like) or a metal roll (SUS roll and the like). Be done. It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

Lamination of the base material and the resin sheet may be carried out by, for example, a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The heat crimping pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

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

Further, the resin composition layer can be formed by, for example, a compression molding method. As the molding conditions, the same conditions as the method for forming the resin composition layer in the step of forming the sealing layer of the semiconductor chip package described later may be adopted.

After forming the resin composition layer on the base material, the resin composition layer is thermosetting to form an insulating layer. The thermosetting conditions of the resin composition layer differ depending on the type of the resin composition, but the curing temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 200 ° C.). The curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is usually at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). May be preheated for usually 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

As described above, a circuit board having an insulating layer can be manufactured. Further, the method of manufacturing the circuit board may further include an arbitrary step.
For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before the thermosetting of the resin composition layer, or may be peeled off 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. For example, the surface of the insulating layer can be polished using a surface grinding machine.

The method for manufacturing a circuit board may include, for example, the step (3) of connecting the conductor layers between layers. In this step (3), the conductor layer provided on one side of the insulating layer (for example, the conductor layer formed on the surface of the base material) is conducted to the other side of the conductor layer. This step (3) may include forming a via hole in the insulating layer, further forming a conductor layer at an appropriate position on the insulating layer including the position where the via hole is formed, and performing interlayer connection. .. Further, the step (3) may include, for example, polishing or grinding the other side of the insulating layer to expose the conductor layer formed on one side of the insulating layer and performing interlayer connection.

When interlayer connection is performed using via holes, for example, after forming via holes in the insulating layer formed on the base material with a wiring layer, a conductor layer is formed on the side opposite to the base material of the insulating layer to correlate the connection. I do. Examples of the method for forming the via hole include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. This laser irradiation can be performed using an appropriate laser processing machine using an arbitrary light source such as a carbon dioxide gas laser, a YAG laser, or an excimer laser. For example, the support side of the resin sheet may be irradiated with a laser to form a via hole that penetrates the support and the insulating layer to expose the conductor layer on the surface of the base material.

Laser irradiation can be carried out by an appropriate process according to the selected laser processing machine. The shape of the via hole is not particularly limited, but is generally circular or substantially circular. The shape of the via hole refers to the shape of the contour of the opening when viewed in the extending direction of the via hole.

After forming the via hole, it is preferable to perform a step of removing smear in the via hole. This process is sometimes referred to as the desmear process. For example, when the conductor layer is formed on the insulating layer by a plating step, the via holes may be subjected to a wet desmear treatment. Further, when the conductor layer is formed on the insulating layer by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Further, the insulating layer may be roughened by the desmear step.

Further, the insulating layer may be roughened before the conductor layer is formed on the insulating layer. According to this roughening treatment, the surface of the insulating layer including the inside of the via hole is usually roughened. As the roughening treatment, either a dry type or a wet type roughening treatment may be performed. Examples of the dry roughening treatment include plasma treatment and the like. Further, as an example of the wet roughening treatment, a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be mentioned in this order.

After forming the via hole, a conductor layer is formed on the insulating layer. By forming the conductor layer at the position where the via hole is formed, the newly formed conductor layer and the conductor layer on the surface of the base material are made conductive, and the interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, and a vapor deposition method, and the plating method is particularly preferable. In a preferred 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 conductor layer having a desired wiring pattern. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Further, the conductor layer may have a single layer structure, or may have a multi-layer structure including two or more layers of different types of materials.

Here, an example of an embodiment in which the conductor layer is formed on the 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 corresponding to a desired wiring pattern. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At that time, along with the formation of the electrolytic plating layer, the via holes may be embedded by electrolytic plating to form a filled via. After forming the electroplating layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by a treatment such as etching to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

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

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

When interlayer connection is performed by polishing or grinding the insulating layer, for example, the insulating layer formed on the base material with a wiring layer is polished or ground, and the conductor layer formed on the base material is used as the base material of the insulating layer. Expose to the opposite side. As a method for polishing and grinding the insulating layer, any method capable of exposing the conductor layer on the surface of the base material can be used. Above all, a method in which a polished surface or a ground surface parallel to the layer plane of the insulating layer can be obtained by polishing or cutting is preferable. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as a buff, a surface grinding method by rotating a grindstone, and the like can be mentioned. Further, when the interlayer connection is performed by polishing or grinding the insulating layer, the smear removal step, the roughening treatment step, and the conductor layer forming step on the insulating layer are performed in the same manner as in the case of the interlayer connection using the via hole. You may. Further, it is not necessary to expose all the conductor layers on the surface of the base material, and a part thereof may be exposed.

The method for manufacturing a circuit board may include, for example, a step (4) of removing a base material. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a base material having a peelable first metal layer and a second metal layer is used. A suitable example will be described below. A conductor layer is formed on the surface of the second metal layer of the base material having the first metal layer and the second metal layer. Further, the resin composition layer is formed on the second metal layer and thermosetting so that the conductor layer is embedded in the resin composition layer to obtain an insulating layer. Then, after making interlayer connections as necessary, the portion of the base material other than the second metal layer is peeled off. Then, the second metal layer is removed by etching with an etching solution such as an aqueous solution of copper chloride. As a result, the base material is removed. At this time, if necessary, the base material may be removed with the conductor layer protected by the protective film.

In other embodiments, the circuit board can be manufactured using a prepreg. The prepreg is a sheet-like fiber base material impregnated with a resin composition by, for example, a hot melt method, a solvent method, or the like. Examples of the sheet-like fiber base material include glass cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric and the like. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, further preferably 700 μm or less, particularly preferably 600 μm or less, and preferably 1 μm or more. It is 1.5 μm or more and 2 μm or more. The thickness of this prepreg can be in the same range as the resin composition layer in the resin sheet described above. The method of manufacturing a circuit board using such a prepreg is basically the same as that of using a resin sheet.

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

As the bonding condition between the circuit board and the semiconductor chip, any condition can be adopted in which the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board can be connected by a conductor. For example, the conditions used in flip-chip mounting of semiconductor chips can be adopted. Further, for example, the semiconductor chip and the circuit board may be bonded to each other via an insulating adhesive.

An example of the joining method is a method of crimping a semiconductor chip to a circuit board. As the crimping conditions, the crimping temperature is usually in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is usually in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

Further, as another example of the joining method, there is a method of reflowing a semiconductor chip onto a circuit board and joining. The reflow condition may be in the range of 120 ° C. to 300 ° C.

After joining the semiconductor chip to the circuit board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-mentioned resin composition may be used, or the above-mentioned resin sheet may be used.

The semiconductor chip package according to the second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition that seals the semiconductor chip. In such a semiconductor chip package, the cured product of the resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include a fan-out type WLP.

FIG. 1 is a cross-sectional view schematically showing a Fan-out type WLP as an example of the semiconductor chip package according to the second embodiment of the present invention. The semiconductor chip package 100 as a Fan-out type WLP is, for example, as shown in FIG. 1, a semiconductor chip 110; a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110; a sealing layer of the semiconductor chip 110. A rewiring forming layer 130 as an insulating layer; a rewiring layer 140 as a conductor layer; a solder resist layer 150; and bumps 160 are provided on the surface opposite to the 120.

The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of forming a sealing layer on a semiconductor chip,
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.
(F) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer, and
(G) A step of forming a solder resist layer on the rewiring layer,
including. Further, the method for manufacturing the semiconductor chip package is as follows.
(H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them may be included. Hereinafter, this manufacturing method will be described in detail.

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

As the base material, for example, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); FR-4 substrate or the like, the glass fiber is impregnated with epoxy resin or the like. Examples thereof include a heat-cured substrate; a substrate made of a bismaleimide triazine resin such as a BT resin; and the like.

As the temporary fixing film, any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

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

(Step (C))
The step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by the cured product of the resin composition described above. The sealing layer is usually formed by a method including a step of forming a resin composition layer on a semiconductor chip and a step of thermally curing the resin composition layer to form a sealing layer.

Taking advantage of the excellent compression moldability of the resin composition, it is preferable that the resin composition layer is formed by a compression molding method. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition in the mold to form a resin composition layer covering the semiconductor chip.
The specific operation of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. Further, the resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition is attached to the lower mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded, and heat and pressure are applied to the resin composition to perform compression molding.
Further, the specific operation of the compression molding method may be as follows, for example. An upper mold and a lower mold are prepared as molds for compression molding. Place the resin composition on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are molded so that the resin composition placed on the lower mold comes into contact with the semiconductor chip attached to 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 appropriate conditions can be adopted so that good sealing is achieved. For example, the temperature of the mold at the time of molding is preferably a temperature at which the resin composition can exhibit excellent compression moldability, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher, and preferably 120 ° C. or higher. It is 200 ° C. or lower, more preferably 170 ° C. or lower, and particularly preferably 150 ° C. or lower. The pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Usually, the mold is removed after the formation of the resin composition layer. The mold may be removed before the thermosetting of the resin composition layer, or after the thermosetting.

The resin composition layer may be formed by laminating a resin sheet and a semiconductor chip. For example, a resin composition layer can be formed on a semiconductor chip by heat-pressing the resin composition layer of the resin sheet and the semiconductor chip. Lamination of the resin sheet and the semiconductor chip can usually be performed by using the semiconductor chip instead of the base material in the same manner as the laminating of the resin sheet and the base material in the method for manufacturing a circuit board.

After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermosetting to obtain a sealing layer covering the semiconductor chip. As a result, the semiconductor chip is sealed with the cured product of the resin composition. The thermosetting conditions of the resin composition layer may be the same as the thermosetting conditions of the resin composition layer in the method for manufacturing a circuit board. Further, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheat treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. As the treatment conditions for this preheat treatment, the same conditions as those for the preheat treatment in the method for manufacturing a circuit board may be adopted.

(Step (D))
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming or expanding the temporary fixing film to peel it off. Further, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through a base material to reduce the adhesive force of the temporary fixing film and peeling the film can be mentioned.

In the method of heating, foaming or expanding the temporary fixing film to peel it off, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Further, in the method for peeling by reducing the adhesive strength of the temporary fixing film by ultraviolet irradiation, irradiation amount of ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

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

As the material of the rewiring cambium, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as this thermosetting resin.

After forming the rewiring cambium, via holes may be formed in the rewiring cambium in order to interconnect the semiconductor chip and the rewiring layer between layers.

In the method of forming a via hole when the material of the rewiring cambium is a photosensitive resin, the surface of the rewiring cambium is usually irradiated with active energy rays through a mask pattern to illuminate the rewiring cambium of the irradiated portion. Let it cure. Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set according to the photosensitive resin. Examples of the exposure method include a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium and exposed, and a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact with the rewiring cambium. Can be mentioned.

After the rewiring cambium is photocured, the rewiring cambium is developed and the unexposed portion is removed to form via holes. The development may be either wet development or dry development. Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

Examples of the method for forming the via hole when the material of the rewiring cambium is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Above all, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine that uses a light source such as a carbon dioxide gas laser, a UV-YAG laser, or an excimer laser.

The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, further preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring cambium.

(Step (F))
The step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the insulating layer in the method of manufacturing a circuit board. Further, the steps (E) and (F) may be repeated, and the rewiring layer and the rewiring forming layer may be alternately stacked (build-up).

(Process (G))
The step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any material having an insulating property can be used. Of these, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention as a thermosetting resin.

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

(Step (H))
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them. The method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

In the semiconductor chip package according to the third embodiment of the present invention, for example, in the semiconductor chip package 100 as shown in FIG. 1, the rewiring forming layer 130 or the solder resist layer 150 is used as a cured product of the resin composition of the present invention. It is a semiconductor chip package formed in.

[14. Semiconductor device]
Semiconductor devices on which the above-mentioned semiconductor chip packages are mounted include, for example, electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example, televisions). , Motorcycles, automobiles, trains, ships, aircraft, etc.) and various semiconductor devices.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Measuring method of epoxy resin viscosity]
In the following examples and comparative examples, the viscosity of the epoxy resin is 45 ° C. using an E-type viscometer (“RE-25U” manufactured by Toki Sangyo Co., Ltd., using a cone rotor of 1 ° 34 ′ × R24). It was measured under the condition of 1 rpm.

[Example 1]
Liquid polybutadiene epoxy resin (“JP-400” manufactured by Nippon Soda Co., Ltd., epoxy equivalent 230, number average molecular weight Mn = 3500, viscosity 5.5 Pa · s at 45 ° C, glass transition temperature -62 ° C), 2 parts, N-phenyl- 90 parts of spherical silica (average particle size 3.5 μm, specific surface area 3.7 m ² / g) surface-treated with 3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.), acid anhydride curing agent ( Shin Nihon Rika Co., Ltd. "HNA-100", acid anhydride equivalent 179) 10 parts, glycidylamine type epoxy resin (ADEKA "EP-3980S", epoxy equivalent 115) 3 parts, glycidylamine type epoxy resin (Mitsubishi Chemical) "630" manufactured by Shikoku Co., Ltd., epoxy equivalent 95) 7 parts, bisphenol A type epoxy resin ("EXA-850CRP" manufactured by DIC, epoxy equivalent 173) 3 parts, imidazole curing accelerator ("2E4MZ" manufactured by Shikoku Kasei Co., Ltd.) 0 . 1 part was mixed with a mixer to obtain a resin composition.

[Example 2]
Instead of 10 parts of the acid anhydride curing agent (“HNA-100” manufactured by New Japan Chemical Co., Ltd.), 5 parts of a cresol novolac type curing agent (“KA-1160” manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent 117) was used.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

[Example 3]
Instead of 10 parts of the acid anhydride curing agent ("HNA-100" manufactured by New Japan Chemical Co., Ltd.), 5 parts of the liquid novolak type phenol curing agent ("MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 141) is used. There was.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

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

[Example 5]
Instead of 10 parts of the acid anhydride curing agent ("HNA-100" manufactured by New Japan Chemical Co., Ltd.), 5 parts of the liquid novolak type phenol curing agent ("MEH-8000H" manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 141) is used. There was.
Further, instead of 7 parts of the glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Corporation), 7 parts of the glycidylamine type epoxy resin (“ELM-100H” manufactured by Sumitomo Chemical Corporation, epoxy equivalent 106) was used.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

[Comparative Example 1]
Instead of two parts of liquid polybutadiene epoxy resin (Nippon Soda "JP-400"), polybutadiene epoxy resin (Nippon Soda "JP-200", epoxy equivalent 210-240, number average molecular weight Mn = 2200, 45 ° C. The viscosity of 100 Pa · s) was used in 2 parts.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

[Comparative Example 2]
Instead of two parts of liquid polybutadiene epoxy resin (Nippon Soda "JP-400"), polybutadiene epoxy resin (Dysel "PB-3600", epoxy equivalent 193, number average molecular weight Mn = 5900, viscosity 45 Pa at 45 ° C. -S) Two parts were used.
Further, instead of 10 parts of the acid anhydride curing agent ("HNA-100" manufactured by New Japan Chemical Co., Ltd.), 5 parts of a cresol novolac type curing agent ("KA-1160" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent 117) is used. There was.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

[Comparative Example 3]
No liquid polybutadiene epoxy resin ("JP-400" manufactured by Nippon Soda Corporation) was used.
In addition, instead of 10 parts of an acid anhydride curing agent ("HNA-100" manufactured by New Japan Chemical Co., Ltd., acid anhydride equivalent 179), a cresol novolac type curing agent ("KA-1160" manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent) 117) 5 parts were used.
Further, the amount of the glycidylamine type epoxy resin (“EP-3980S” manufactured by ADEKA, epoxy equivalent 115) was changed from 3 parts to 5 parts.
Except for the above items, the same operation as in Example 1 was carried out to obtain a resin composition.

[Measurement of linear thermal expansion coefficient (CTE) of cured product of resin composition]
(Preparation of cured product for evaluation)
A polyethylene terephthalate film (“501010” manufactured by Lintec Corporation, thickness 38 μm, 240 mm square) with a mold release treatment on one side was prepared. A glass cloth base material epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Electric Works, thickness 0.7 mm, 255 mm square) was laminated on the untreated surface of this polyethylene terephthalate film. The four sides were fixed with a polyimide adhesive tape (width 10 mm). As a result, a fixed PET film containing a polyethylene terephthalate film and a glass cloth-based epoxy resin double-sided copper-clad laminate was obtained.

Methyl ethyl ketone was added to the resin compositions produced in Examples and Comparative Examples to dilute them, and the viscosity of the resin composition was adjusted to 4000 mPa · s. In addition, as a support, a polyethylene terephthalate film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point) whose surface is subjected to a mold release treatment with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). 130 ° C.) was prepared. The resin composition whose viscosity was adjusted as described above was applied onto this support using a die coater so that the thickness of the resin composition layer after drying was 100 μm. The applied resin composition layer was dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 10 minutes to obtain a resin sheet containing the support and the resin composition layer.

Each resin sheet (thickness of the resin composition layer 100 μm) was cut into a square of 200 mm square. The cut resin sheet is subjected to a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and the resin composition layer is fixed on the surface of the PET film on the polyethylene terephthalate film side (that is,). , A multi-layer sample was obtained by laminating so as to be in contact with the center of the surface subjected to the mold release treatment. The above-mentioned laminating was carried out by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, the obtained multilayer sample was put into an oven at 100 ° C. and heated for 30 minutes, and then transferred to an oven at 175 ° C. and heated for 30 minutes to heat-cure the resin composition layer. Then, the multi-layer sample was taken out under a room temperature atmosphere, the support was peeled off, and then the sample was placed in an oven at 190 ° C. and heated for 90 minutes to further heat-cure the resin composition layer. The obtained multi-layer sample contained a cured product layer in which the resin composition layer was cured, a polyethylene terephthalate film, and a glass cloth-based epoxy resin double-sided copper-clad laminate in this order.

After the above-mentioned thermosetting, the polyimide adhesive tape was peeled off, the glass cloth base material epoxy resin double-sided copper-clad laminate was removed, and the polyethylene terephthalate film was further peeled off to obtain a cured product of a sheet-shaped resin composition. The obtained cured product may be referred to as an "evaluation cured product".

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

[Measurement of warpage amount]
The resin compositions produced in Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) to obtain a thickness. A resin composition layer having a thickness of 300 μm was formed. Then, it heated at 180 degreeC for 90 minutes, and the resin composition layer was thermoset. As a result, a sample substrate containing a silicon wafer and a cured product layer of the resin composition was obtained.

Using a shadow moire measuring device (“Thermoire AXP” manufactured by Akorometrix), 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. The measurement was performed in accordance with the Japan Electronics and Information Technology Industries Association standard JEITA EDX-7311-24. Specifically, the virtual plane calculated by the least squares method of all the data on the substrate surface of the measurement region was used as a reference plane, and the difference between the minimum value and the maximum value in the vertical direction from the reference plane was obtained as the warp amount. A warp amount of less than 2 mm was judged as "◯", and a warp amount of 2 mm or more was judged as "x".

[Evaluation of adhesion]
A thermal release tape (Thermal release tape; "Riva Alpha" manufactured by Nitto Denko KK), which has adhesiveness at room temperature and can be easily peeled off when heated, was attached to a 12-inch silicon wafer. On this heat release sheet, 100 1 cm square silicon chips (thickness 400 μm) were placed at equal intervals. Subsequently, the resin compositions produced in Examples and Comparative Examples were placed on a heat-release sheet on which a silicon chip was placed, and a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) was applied. A resin composition layer having a layer thickness of 500 μm in which a silicon chip was embedded was formed by compression molding using the product. The heat release sheet and the silicon wafer were removed by heating at 180 ° C. to make the heat release sheet removable. Then, the resin composition layer was heated at 180 ° C. for 90 minutes to thermoset the resin composition layer. As a result, a resin wafer containing a cured product layer of the resin composition and a silicon chip embedded in the cured product layer was obtained.

Then, a thermal cycle test of the resin wafer was carried out. This thermal cycle test is a test in which cooling to −55 ° C. and heating to 125 ° C. are set as one cycle, and the above cooling and heating are repeated for 1000 cycles. After the thermal cycle test, the resin wafer was observed, and the case where delamination occurred at the interface between the silicon chip and the cured product layer was judged as “x”, and the case where delamination did not occur was judged as “◯”. Further, when a crack was generated on the surface of the resin composition layer after compression molding of the resin composition, it was determined as "crack".

[Evaluation of compression moldability]
The resin compositions produced in Examples and Comparative Examples were compression-molded on a 12-inch silicon wafer using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) to obtain a thickness. A resin composition layer having a thickness of 300 μm was formed. After that, the resin composition layer was observed, and the case where the resin composition could be filled up to the end of the wafer was "○", the case where unfilling occurred was "x", and the surface of the resin composition layer was cracked after compression molding. When it occurred, it was judged as "crack".

[Measurement method of dielectric loss tangent]
The resin compositions produced in Examples and Comparative Examples were placed on a SUS plate whose surface was subjected to a mold release treatment using a compression molding device (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes). And compression molding was performed to form a resin composition layer having a thickness of 300 μm. The SUS plate was peeled off, and the resin composition layer was heat-cured by heating at 180 ° C. for 90 minutes to obtain a cured product layer of the resin composition. This cured product layer was cut out to a length of 80 mm and a width of 2 mm to obtain an evaluation sample for dielectric loss tangent measurement. For this evaluation sample, the dielectric positive contact was measured at a measurement temperature of 23 ° C. and a measurement frequency of 5.8 GHz by a cavity resonance perturbation method using an analyzer (“HP8362B” manufactured by Agilent Technologies).

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in the table below. In the table below, the meanings of the abbreviations are as follows.
JP400: Liquid polybutadiene epoxy resin (“JP-400” manufactured by Nippon Soda Corporation, epoxy equivalent 230, number average molecular weight Mn = 3500, viscosity 5.5 Pa · s at 45 ° C.).
JP200: Polybutadiene epoxy resin (“JP-200” manufactured by Nippon Soda Corporation, epoxy equivalent 210-240, number average molecular weight Mn = 2200, viscosity 100 Pa · s at 45 ° C.).
PB3600: Polybutadiene epoxy resin (“PB-3600” manufactured by Daicel Corporation, epoxy equivalent 193, number average molecular weight Mn = 5900, viscosity 45 Pa · s at 45 ° C.).
HNA-100: Acid anhydride curing agent (“HNA-100” manufactured by New Japan Chemical Co., Ltd., acid anhydride equivalent 179).
KA-1160: Cresol novolac type curing agent (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl group equivalent 117).
MEH-8000H: Liquid novolak type phenol curing agent (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 141).
EP-3980S: Glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA Corporation, epoxy equivalent 115). Liquid YED-216D: Aliphatic epoxy resin (“YED-216D” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 120). Liquid 630: Glysidylamine type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 95). Liquid EXA-850CRP: Bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC Corporation, epoxy equivalent 173). Liquid ELM-100H: Glycidylamine type epoxy resin (“ELM-100H” manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 106).
2E4MZ: Imidazole-based curing accelerator ("2E4MZ" manufactured by Shikoku Chemicals Corporation).

[Consideration]
As can be seen from Table 1, the resin compositions according to the examples are excellent in compression moldability. Further, the cured product of the resin composition according to the examples has a low coefficient of linear thermal expansion, can suppress warpage, and is excellent in high adhesion even after repeated heating and cooling. Therefore, according to the present invention, a resin composition layer having a low coefficient of linear thermal expansion, capable of suppressing warpage, a cured product having high adhesion even after repeated heating and cooling, and excellent compression moldability can be obtained. It was confirmed that
Further, by comparing Comparative Example 3 in which the epoxy resin having an alkene skeleton in the molecule is not used with Examples, according to the resin composition of the present invention in which the epoxy resin having an alkene skeleton in the molecule is used. It was confirmed that a cured product having a low dielectric loss tangent is usually obtained.
Further, in Examples 1 to 5, it has been confirmed that even when the components (D) to (E) are not contained, the results are the same as those in the above-mentioned Examples, although the degree is different. ..

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulation layer 130 Rewiring cambium 140 Rewiring layer 150 Solder resist layer 160 Bump

Claims (18)

(A) An epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C., a number average molecular weight of 2500 or more, and an alkene skeleton in the molecule.
(B) an inorganic filler, and (C) a curing agent seen including,
A resin composition in which the content of the component (A) is 0.2% by mass to 10% by mass with respect to 100% by mass of the non-volatile component of the resin composition. The resin composition according to claim 1 , further comprising (D) an epoxy resin other than the component (A). The resin composition according to claim 2 , wherein the amount of the component (D) is 500 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the component (A). (A) An epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C., a number average molecular weight of 2500 or more, and an alkene skeleton in the molecule.
(B) Inorganic filler ,
(C) Hardener and
The component (A) other than the (D) an epoxy resin observed including,
A resin composition in which the amount of the component (D) is 500 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the component (A) . The resin composition according to any one of claims 1 to 4 , wherein the component (A) has a polybutadiene structure in the molecule. The resin composition according to any one of claims 1 to 5, wherein the component (A) has a viscosity of 15 Pa · s or less at 45 ° C. The resin composition according to any one of claims 1 to 6 , wherein the average particle size of the component (B) is 0.1 μm to 10 μm. The resin composition according to any one of claims 1 to 7 , wherein the component (C) is an acid anhydride-based curing agent or a phenol-based curing agent. The resin composition according to any one of claims 1 to 8, further comprising (E) a curing accelerator. Any one of claims 1 to 9, wherein the cured product obtained by heating the resin composition at 190 ° C. for 90 minutes has a linear thermal expansion coefficient of 10 ppm / ° C. or less in the range of 25 ° C. to 150 ° C. The resin composition according to the item. The resin composition according to any one of claims 1 to 10, wherein the cured product obtained by heating the resin composition at 180 ° C. for 90 minutes has a dielectric loss tangent of 0.007 or less. The resin composition according to any one of claims 1 to 11 , which is a resin composition for encapsulating a semiconductor or an insulating layer. The resin composition according to any one of claims 1 to 12 , which is a resin composition for a Fan-out type WLP or a Fan-out type PLP. The resin composition according to any one of claims 1 to 13 , which is a liquid resin composition. A resin sheet having a support and a resin composition layer containing the resin composition according to any one of claims 1 to 14 provided on the support. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 14 . A semiconductor chip package including the circuit board according to claim 16 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 14 for sealing the semiconductor chip.

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