JP2019014843A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition having a low coefficient of linear thermal expansion, capable of suppressing warpage, obtaining a cured product having high adhesion even after repeated heating and cooling, and having excellent compression moldability. A resin composition comprising (A) an epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C. and having an alkene skeleton in the molecule, (B) an inorganic filler, and (C) a curing agent. . [Selection figure] None

Description

  The present invention relates to a resin composition. 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 increased, and accordingly, the semiconductor chip package insulating layer used in these small electronic devices is required to have higher functionality. . As such an insulating layer, what is formed by hardening | curing a resin composition is known, for example (refer patent document 1 and 2).

JP 2014-55233 A International Publication No. 2014/157446

  The insulating layer is required to have a low dielectric loss tangent in order to reduce electric signal loss. As a result of investigation, 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 inventors, it has been found that a resin composition containing an epoxy resin having an alkene skeleton in the molecule has low compression moldability. When a resin composition having low compression moldability is to be formed by a compression molding method, it is difficult to fill the resin composition in every corner.

  In recent years, there has been a demand for a smaller semiconductor chip package, and accordingly, an insulating layer used for the semiconductor chip package is required to be thinner. For this reason, it is desired to develop an insulating layer that has a low coefficient of linear thermal expansion (sometimes referred to as CTE or thermal expansion coefficient) and can suppress warpage. Furthermore, the insulating layer is required to have high adhesion even after repeated heating and cooling. For example, an insulating layer that is in close contact with a silicon chip is unlikely to be peeled off from the silicon chip even after repeated heating and cooling. Is required. However, a conventional resin composition containing an epoxy resin having an alkene skeleton in the molecule has not achieved satisfactory performance in the evaluation of linear thermal expansion coefficient, 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-described problems are also caused when the resin composition is used as a sealing material for a semiconductor chip package.

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

As a result of intensive studies to solve the above problems, the present inventor has (A) an epoxy resin having a predetermined range of viscosity at 45 ° C. and having an alkene skeleton in the molecule, (B) an inorganic filler, And (C) It discovered that the said subject could be solved with the resin composition containing combining a hardening | curing agent, and completed this invention.
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 having an alkene skeleton in the molecule;
A resin composition comprising (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] The content of the component (A) is 0.2% by mass to 10% by mass with respect to 100% by mass of the nonvolatile component of the resin composition, according to any one of [1] to [3] The resin composition as 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 curing agent or a phenol curing agent.
[7] The resin composition according to any one of [1] to [6], further including (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 semiconductor encapsulation or insulating layer.
[10] The resin composition according to any one of [1] to [9], which is a liquid resin composition.
[11] A resin sheet comprising a support and a resin composition layer comprising 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 comprising the circuit board according to [12] and a semiconductor chip mounted on the circuit board.
[14] A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of [1] to [10], which seals the semiconductor chip.

  According to the present invention, a resin composition having a low linear thermal expansion coefficient, capable of suppressing warpage, obtaining 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 including the resin composition; a circuit board including an insulating layer formed of a cured product of the resin composition; and a semiconductor chip package including a 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 a semiconductor chip package according to a 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 following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

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

[1. Outline of Resin Composition]
The resin composition of the present invention comprises (A) an epoxy resin having a predetermined range of viscosity 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 predetermined range of viscosity at 45 ° C. and having an alkene skeleton in the molecule” as the component (A) may be referred to as “(A) epoxy resin”.

  By including the (A) component, the (B) component, and the (C) component in combination, the resin composition is excellent in compression moldability, has a low linear thermal expansion coefficient, can suppress warpage, The desired effect of the present invention can be obtained that a cured product that can exhibit high adhesion even when cooling is repeated can be obtained. The cured product of this resin composition can be preferably used as an insulating layer and a sealing material of a semiconductor chip package, taking advantage of its excellent characteristics.

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

[2. (A) Epoxy resin]
(A) The epoxy resin has a predetermined range of viscosity at 45 ° C. (A) The specific viscosity of the epoxy resin 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 (A) epoxy resin having such a viscosity, the compression moldability of the resin composition can be improved. Furthermore, by using the (A) epoxy resin having such a viscosity, it is possible to obtain a cured product that has a low coefficient of linear thermal expansion, can suppress warping, and can exhibit high adhesion even when heating and cooling are repeated. it can. (A) 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.

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

  In addition, (A) the epoxy resin has an alkene skeleton in the molecule. Here, the alkene skeleton indicates a structure represented by the following formula (1). Although there is no restriction | limiting in the atom to which the bond of the carbon atom shown by Formula (1) couple | bonds, Usually, they are a hydrogen atom or a carbon atom. Thus, by using the (A) epoxy resin having an alkene skeleton, the dielectric loss tangent of the cured product of the resin composition can be generally lowered. Furthermore, it is usually possible to improve the insulation of the cured product or to reduce 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 is present in both the main chain and the side chain of the molecule. It may have an alkene skeleton. Among these, 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 reducing the dielectric loss tangent of the cured product.

  The (A) epoxy resin having an alkene skeleton usually contains a structural unit having an alkene skeleton in the molecule. The structural unit is preferably a divalent hydrocarbon group having an alkene skeleton from the viewpoint of remarkably obtaining the desired effect of the present invention and effectively reducing the dielectric loss tangent of the cured product. The divalent aliphatic hydrocarbon group is more preferable, and the 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 from the viewpoint of remarkably 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 effectively reducing the dielectric loss tangent of the cured product. The number of carbon atoms of the alkenyl group is usually 2 or more, preferably 6 or less, more preferably from the viewpoint of remarkably 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 alkenyl groups include vinyl groups, 1-propenyl groups, 2-propenyl groups, and the like.

  Preferred examples of the structural unit having an alkene skeleton include structural units 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 reducing the dielectric loss tangent of the cured product.

  (A) The number of the structural units having the 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 structural unit having an alkene skeleton as a repeating unit in the molecule. It is preferable to include two or more.

  In particular, the (A) epoxy resin preferably has a polybutadiene structure in the molecule from the viewpoint of remarkably obtaining the desired effect of the present invention and effectively reducing 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. Especially, it is preferable that (A) epoxy resin contains two or more structural units represented by Formula (2) in one molecule.

  Furthermore, it is preferable that the number of structural units represented by formula (2) per molecule of (A) epoxy resin is larger than the number of structural units represented by formula (3). Thereby, 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 adhesiveness of the cured product when heating and cooling are repeated. Can be effectively increased.

  The (A) epoxy resin 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 both in the main chain and the side chain of the molecule. You may have an epoxy group. Especially, it is preferable to have an epoxy group in the side chain of the molecule | numerator from a viewpoint which obtains the desired effect of this invention notably, and a viewpoint of making the dielectric loss tangent of hardened | cured material effective low.

  (A) Although the epoxy resin may have an epoxy group in the structural unit having an alkene skeleton, the viewpoint that the desired effect of the present invention is remarkably obtained and the dielectric loss tangent of the cured product are effectively reduced. From this viewpoint, it is preferable to have an epoxy group in a structural unit different from the 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 from the viewpoint of remarkably 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 structural units 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). Moreover, the structural unit represented by Formula (5) can be formed, for example, by epoxidizing polybutadiene containing the structural unit represented by Formula (3). Among these, the structural unit represented by Formula (4) is preferable from the viewpoint of significantly obtaining the desired effect of the present invention and from the viewpoint of effectively reducing the dielectric loss tangent of the cured product.

  Furthermore, it is preferable that the number of structural units represented by formula (4) per molecule of (A) epoxy resin is larger than the number of structural units represented by formula (5). Thereby, 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 adhesiveness of the cured product when heating and cooling are repeated. Can be effectively increased.

  (A) It is preferable that an epoxy resin has two or more epoxy groups in a molecule | numerator from a viewpoint which obtains the desired effect of this invention notably. Moreover, it is preferable that (A) epoxy resin is an aliphatic epoxy resin which does not contain an aromatic ring in a molecule | numerator from a viewpoint which obtains the desired effect of this invention notably.

  (A) If the example of the molecular structure of an epoxy resin is given, what is shown to Formula (6) will be mentioned, for example. In formula (6), m and n each independently represent a natural number.

  (A) As a specific example of an epoxy resin, “JP400” manufactured by Nippon Soda Co., Ltd. having the molecular structure represented by the formula (6) can be given. Moreover, (A) component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  In general, an epoxy resin may be an epoxy resin that is liquid at a temperature of 20 ° C. (hereinafter sometimes referred to as “liquid epoxy resin”) and an epoxy resin that is a solid at a temperature of 20 ° C. (“solid epoxy resin”). ). (A) The epoxy resin may be a solid epoxy resin, but is preferably a liquid epoxy resin. (A) When the epoxy resin 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.

  (A) The number average molecular weight Mn of the epoxy resin 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 not less than the lower limit of the above range, the compression molding property of the resin composition is particularly improved, or the linear thermal expansion coefficient of the cured product of the resin composition is effectively improved. The ability of the cured product to be lowered, to suppress warpage can be effectively enhanced, and peeling of the cured product by heating and cooling can be effectively suppressed. In addition, (A) the number average molecular weight Mn of the epoxy resin is not more than the upper limit of the above range, the compression molding property of the resin composition is particularly improved, or the linear thermal expansion coefficient of the cured product of the resin composition is effective. It is possible to reduce the number of cracks, and to increase the toughness of the cured product of the resin composition, thereby effectively suppressing the occurrence of cracks.

  (A) The weight average molecular weight Mw of the epoxy resin is preferably 5000 to 60000, more preferably 6000 to 50000, and still more preferably 7000 to 20000 from the viewpoint of remarkably obtaining the desired effect of the present invention.

  The number average molecular weight Mn and the weight average molecular weight Mw of the resin can be measured as values in terms of polystyrene by gel permeation chromatography (GPC). For example, the number average molecular weight Mn and 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 KK 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.

  (A) The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. (A) When the epoxy equivalent of an epoxy resin exists in the said range, the crosslinked density of the hardened | cured material of a resin composition increases, and an insulating layer with small surface roughness can be obtained. Epoxy equivalent is the mass of resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

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

  The amount of the (A) epoxy resin in the resin composition is preferably 0.2% by mass or more with respect to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. Preferably it is 0.3 mass% or more, Especially preferably, it is 0.4 mass% or more, Preferably it is 10 mass% or less, More preferably, it is 9.5 mass% or less, Most preferably, it is 9 mass% or less. Moreover, the dielectric loss tangent of the hardened | cured material of a resin composition can be normally lowered | hung by keeping the quantity of (A) epoxy resin in the said range.

[3. (B) Inorganic filler]
The resin composition contains an inorganic filler as the component (B). (B) By using an inorganic filler, the linear thermal expansion coefficient of the hardened | cured material of a resin composition can be made small, and curvature can be suppressed.

  (B) An inorganic compound is used as the material of the inorganic filler. (B) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, spherical silica is preferable as the silica. (B) An inorganic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  Usually, the (B) 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 diameter of an inorganic filler exists in the said range, the desired effect of this invention can be acquired notably. In particular, when the average particle size of the (B) inorganic filler 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. Moreover, the adhesiveness of the hardened | cured material at the time of repeating a heating and cooling can be improved effectively. Moreover, (B) When the average particle diameter of an inorganic filler exists in the said range, when forming an insulating layer with the hardened | cured material of a resin composition, the surface roughness of an insulating layer can be made low normally.

  (B) The average particle diameter of particles such as inorganic fillers can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles can be created on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the average particle size can be measured as the median diameter from the particle size distribution. As the measurement sample, particles in which particles are dispersed in a solvent such as water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

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

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

  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 manufactured by Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxy) Silane), “KBM5783” (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “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. ( Chain epoxy type silane coupling agent), and the like. Of these, a nitrogen atom-containing silane coupling agent is preferable, an aminosilane-based coupling agent containing a phenyl group is more preferable, N-phenyl-3-aminoalkyltrimethoxysilane is further preferable, and N-phenyl-3-aminopropyl is more preferable. Trimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane are more preferred. Moreover, a surface treating agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The degree of the surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (B) 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 the melt viscosity of the resin composition and the increase in melt viscosity in the form of a sheet, 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.

  (B) The amount of carbon per unit surface area of the inorganic filler is determined by washing the surface-treated (B) inorganic filler with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as “MEK”)). Can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the (B) inorganic filler surface-treated with the surface treatment agent are mixed and ultrasonically cleaned at 25 ° C. for 5 minutes. Then, after removing a supernatant liquid and drying solid content, the amount of carbon per unit surface area of (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, and still more preferably 70% by mass with respect to 100% by mass of the nonvolatile component in the resin composition. Further, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 86% by mass or less. (B) When the quantity of an inorganic filler exists in the said range, the desired effect of this invention can be acquired notably, and especially the linear thermal expansion coefficient of a resin composition can be made low effectively.

[4. (C) Curing agent]
The resin composition contains a curing agent as the component (C). The (C) curing agent usually has a function of curing the resin composition by reacting with an epoxy resin such as (A) an epoxy resin or (D) an epoxy resin. (C) A hardening | curing agent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  (C) As the curing agent, a compound capable of reacting with an epoxy resin and curing the resin composition can be used. For example, an acid anhydride curing agent, a phenol curing agent, an active ester curing agent, Examples include cyanate ester-based curing agents, benzoxazine-based curing agents, and carbodiimide-based curing agents. Among these, acid anhydride type curing agents and phenol type curing agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention.

  Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid Anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tri Mellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hex Hydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis (anhydrotrimellitate), styrene and maleic acid And polymer type acid anhydrides such as styrene / maleic acid resin copolymerized.

  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. Among these, a compound having a hydroxyl group bonded to a benzene ring is preferable. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a novolak structure is preferred. Furthermore, 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, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7851”, “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 ” " Gun Ei Chemical Industry Co., Ltd. of "GDP-6115L", "GDP-6115H", "ELPC75", and the like.

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

  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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester 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 benzoylated product of phenol novolac. The active ester compound containing is mentioned. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

  As a commercial product of an active ester type curing agent, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000”, “HPC-8000H”, “ 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” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; Made) “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent which is an acetylated product of phenol novolak; “YLH1026” (manufactured by Mitsubishi Chemical Corporation), “YLH1030” (manufactured by Mitsubishi Chemical Corporation) Mitsubishi Chemical Corporation), “YLH1048” (Mitsubishi Chemical Corporation);

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac; prepolymer these cyanate resin is partially triazine of; and the like. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan; “ULL-950S” (polyfunctional cyanate ester resin); BA230 "," BA230S75 "(a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer); and the like.

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

  Specific examples of the carbodiimide 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, with respect to 100% by mass of the resin component in the resin composition, from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 10% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less.

  When the number of epoxy groups in the epoxy resin including (A) epoxy resin and (D) epoxy resin is 1, the number of active groups in (C) the curing agent is preferably 0.1 or more, more preferably 0.2 or more, and further Preferably it is 0.3 or more, preferably 2 or less, more preferably 1.8 or less, still more preferably 1.6 or less, particularly preferably 1.4 or less. Here, the “number of epoxy groups in the epoxy resin” is a value obtained by adding up all values obtained by dividing the mass of the nonvolatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Further, “(C) the number of active groups of the curing agent” is a value obtained by adding up all values 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 curing agent (C) when the number of epoxy groups of the epoxy resin is 1 is in the above range, the desired effect of the present invention can be remarkably obtained. The heat resistance of the cured product is further improved.

[5. (D) Any epoxy resin]
The resin composition may contain (D) epoxy resin other than the above-mentioned (A) epoxy resin as an arbitrary component.
(D) Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol types. 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 resins, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

  It is preferable that a resin composition contains the epoxy resin which has a 2 or more epoxy group in 1 molecule as (D) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% with respect to 100% by mass of the nonvolatile component (D) of the epoxy resin. % Or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

  (D) As an epoxy resin, a liquid epoxy resin may be used, a solid epoxy resin may be used, and a liquid epoxy resin and a solid epoxy resin may be used in combination. Especially, it is preferable to use a liquid epoxy resin as (D) epoxy resin from a viewpoint of improving the compression moldability of a resin composition.

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

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, aliphatic epoxy resin, and epoxy resin having butadiene structure, bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxy resin Is more preferable.

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

  The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule.

  Solid epoxy resins include bixylenol 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, 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, bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin and 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; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200" (dicyclopentadiene type epoxy resin) manufactured by DIC; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (manufactured by DIC) Naphthylene ether type epoxy resin) “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. Resin); “NC7000L” (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku; “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku; Nippon Steel & Sumitomo Metal "ESN475V" (naphthalene type epoxy resin) manufactured by Chemical Co .; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co .; "YX4000H", "YX4000", "YL6121" (biphenyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-" manufactured by Osaka Gas Chemical Co., Ltd. 500 ";" YL7760 "(bis "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" manufactured by Mitsubishi Chemical Corporation (Tetra) Phenylethane type epoxy resin). These may be used alone or in combination of two or more.

  (D) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, their quantitative 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 between the liquid epoxy resin and the solid epoxy resin is within such a range, usually, when used in the form of a resin sheet, appropriate tackiness is brought about. Moreover, normally, when using with the form of a resin sheet, sufficient flexibility is acquired and a handleability improves. Furthermore, usually, a cured product having a sufficient breaking strength can be obtained.

  (D) The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention.

  (D) The epoxy equivalent of the epoxy resin preferably falls within the same range as described as the range of the epoxy equivalent of (A) the epoxy resin.

  When the resin composition contains (D) an epoxy resin, the amount of (D) the 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 the (A) epoxy resin. The amount 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. (D) By keeping the amount of the epoxy resin within the above range, the desired effect of the present invention can be remarkably obtained.

  When the resin composition contains (D) an epoxy resin, the amount of (D) the epoxy resin is preferably 0.3% by mass or more, more preferably 0 when the nonvolatile component in the resin composition is 100% by mass. 0.5% 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, and further preferably 14% by mass or less. (D) By keeping the amount of the epoxy resin within the above range, the mechanical strength and insulation reliability of the cured product of the resin composition can be increased.

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

  (E) As a hardening accelerator, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator etc. are mentioned, for example. Among these, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2 -Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-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-phenylimidazole compounds of imidazoline and the like and an imidazole compound and adduct of the epoxy resin. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation; “2E4MZ” manufactured by Shikoku Kasei Co., Ltd.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like. Of these, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. 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, and zinc stearate.

  When the resin composition contains (E) a curing accelerator, the amount of (E) the curing accelerator is based on 100% by mass of the resin component of the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. 0.01 mass%-3 mass% are preferable, 0.03 mass%-1.5 mass% are more preferable, 0.05 mass%-1 mass% are more preferable.

[7. (F) Optional additive]
The resin composition may further contain an optional additive as an optional component in addition to the components described above. Examples of such additives include organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; thermoplastic resins; thickeners; antifoaming agents; leveling agents; Resin additives such as colorants, flame retardants, and the like. These additives may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Although the resin composition mentioned above may contain a solvent as needed, it is preferable that it is a solventless resin composition which does not contain a solvent. Thus, even if it does not contain a solvent, (A) the said resin composition containing an epoxy resin can be fluidized when molding using a compression molding method, and can realize excellent compression moldability. . Therefore, this resin composition can be used as a solvent-free resin composition.

[8. Method for producing resin composition]
A resin composition can be manufactured by the method of stirring a compounding component using stirring apparatuses, such as a rotary mixer, for example.

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

Moreover, according to the resin composition mentioned above, the hardened | cured material with a low linear thermal expansion coefficient can be obtained. Therefore, an insulating layer and a sealing layer having a low linear thermal expansion coefficient can be obtained by using this resin composition.
For example, using the resin composition described above, a cured product for evaluation is produced by the method described in Examples, and the linear thermal expansion coefficient of the cured product for evaluation is measured. In this case, the linear thermal expansion coefficient obtained is usually 10 ppm / ° C. or less, preferably 9 ppm / ° C. or less, more preferably 8 ppm / ° C. or less. The lower limit is not particularly limited and is usually 0 ppm / ° C., preferably 1 ppm / ° C. or higher.

Moreover, according to the resin composition mentioned above, the layer of the hardened | cured material which can suppress curvature can be obtained. Therefore, by using this resin composition, it is possible to obtain an insulating layer and a sealing layer that can suppress warping 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 the examples, thereby preparing a sample substrate. In this case, when the sample substrate is heated and cooled in the order of 35 ° C., 260 ° C. and 35 ° C., the amount of warpage measured by the method described in the examples can be usually less than 2 mm.

Moreover, according to the resin composition mentioned above, the hardened | cured material which can exhibit high adhesiveness can be obtained even if heating and cooling are repeated. Therefore, by using this resin composition, it is possible to obtain an insulating layer or a sealing layer that hardly causes peeling 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 manufactured by the method described in the examples. When a thermal cycle test is performed on the resin wafer by the method described in the examples, the occurrence of delamination at the interface between the silicon chip and the cured product layer can be normally suppressed.

The inventor presumes the mechanism by which the resin composition of the present invention can obtain the above-described advantages as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
Since the resin composition mentioned above contains the low viscosity (A) epoxy resin, it is excellent in fluidity at the time of compression molding. Therefore, since the resin composition can easily enter even a small gap, excellent compression moldability is achieved.
In addition, 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. Furthermore, since the (A) epoxy resin can function as a soft flexible component after the resin composition is cured, it can absorb volume changes due to temperature changes. Therefore, the linear thermal expansion coefficient of the cured product of the resin composition can be lowered.
Further, as described above, since the inorganic filler (B) has a small degree of expansion and contraction due to a temperature change, even if a temperature change occurs, the stress caused by the temperature change can be reduced. In addition, since (A) the epoxy resin can function as a soft flexible component after the resin composition is cured, even if stress occurs in the cured product, the (A) epoxy resin can absorb the stress. Therefore, since the generation of stress that can cause warping can be suppressed, warpage can be suppressed.
Furthermore, since the resin composition is excellent in fluidity as described above, residual stress after molding of the resin composition hardly remains. Moreover, even if stress arises by a temperature change, the (A) epoxy resin can absorb the stress as mentioned 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 due to temperature change, so that the occurrence of delamination due to resin failure can be suppressed.

Usually, the cured product of the resin composition has a low dielectric loss tangent. Therefore, an insulating layer having a low dielectric loss tangent can be obtained by using this resin composition.
For example, the hardened | cured material layer of a resin composition is manufactured by the method as described in an Example. The dielectric loss tangent of this cured product layer measured by the measurement method described in the examples is preferably 0.007 or less, more preferably 0.006 or less. The lower limit of the dielectric loss tangent value is preferably as low as possible, and may be, for example, 0.001 or more.

  The resin composition may be liquid or solid, but 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 compression molding at room temperature without special temperature adjustment, and molded by compression molding by heating to an appropriate temperature. May be performed. In addition, since a resin composition that is solid at normal temperature can usually be made liquid by adjusting its temperature to a higher temperature (for example, 130 ° C.), it can be molded by compression molding by appropriate temperature adjustment such as heating. Is possible. Even if the said resin composition does not contain a solvent normally, it can become a liquid state at suitable temperature, for example, it can be used as a liquid sealing material.

[10. Application of resin composition]
The sealing layer and the insulating layer can be formed from the cured product of the resin composition by utilizing the advantages described above. Therefore, this resin composition can be used as a resin composition for semiconductor encapsulation or insulating layer.

  For example, the resin composition includes 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 (resin composition for an insulating layer of a circuit board) for forming an insulating layer.

  For example, the resin composition can be suitably used as a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip).

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

  The resin composition may be used as an underfill material. For example, the resin composition may be used as a MUF (Molding Under Filling) material used after a semiconductor chip is connected to a substrate.

  Furthermore, 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 or prepreg, a solder resist, a die bonding material, a hole-filling resin, or a component-embedded resin.

[11. Resin sheet]
The resin sheet of this invention has a support body and the resin composition layer provided on this support body. A resin composition layer is a layer containing the resin composition of this invention, and is normally formed with the resin composition.

  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 from the viewpoint of thinning. The minimum of the thickness of a resin composition layer is not specifically limited, For example, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). Polyester) such as polycarbonate; acrylic polymer such as polymethyl methacrylate (hereinafter sometimes abbreviated as “PMMA”); cyclic polyolefin; triacetyl cellulose (hereinafter referred to as “PMMA”). May be abbreviated as “TAC”); polyether sulfide (hereinafter may be abbreviated as “PES”); polyether ketone; polyimide; Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil. Among 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.). It may be used.

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents. In addition, examples of the support with a release layer include “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, 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. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The resin sheet can be produced, for example, by applying the resin composition onto a support using an application 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 this resin varnish may be applied to produce a resin sheet. By using the solvent, the viscosity can be adjusted and the coating property can be improved. When the 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; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols 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; An organic solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

  Drying may be performed by a known method such as heating or hot air blowing. The drying condition is 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. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  The resin sheet may contain arbitrary layers other than a support body and a resin composition layer as needed. For example, in the resin sheet, a protective film according 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. By the protective film, it is possible to prevent dust and the like from being attached 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. In addition, the resin sheet can be stored in a roll shape.

  The resin sheet can be suitably used for forming an insulating layer in manufacturing a semiconductor chip package (insulating resin sheet for 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 a package using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

  Moreover, the resin sheet can be suitably used for sealing a semiconductor chip (resin sheet for sealing a semiconductor chip). Examples of applicable semiconductor chip packages include Fan-out type WLP, Fan-in type WLP, Fan-out type PLP, Fan-in type PLP, and the like.

  Moreover, you may use a resin sheet for the material of MUF used after connecting a semiconductor chip to a board | substrate.

  Furthermore, the resin sheet can be used for a wide variety of other applications that require high insulation reliability. 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 step (1) and step (2).
(1) The process 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 substrate is prepared. Examples of the substrate include glass epoxy substrates, metal substrates (stainless steel, cold rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Moreover, the base material may have metal layers, such as copper foil, on the surface as a part of the said base material. For example, you may use the base material which has the 1st metal layer and the 2nd metal layer which can peel on both surfaces. When such a base material is used, a conductor layer as a wiring layer that can function as circuit wiring is usually formed on the surface of the second metal layer opposite to the first metal layer. As a base material having such a metal layer, for example, an ultrathin copper foil with a carrier copper foil “Micro Thin” manufactured by Mitsui Mining & Smelting Co., Ltd. may be mentioned.

  Moreover, the conductor layer may be formed in the surface of one or both of a 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 referred to as a “base material with a wiring layer” as appropriate. The conductive material contained in the conductive layer is, 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. Examples include materials containing the above metals. As the conductive material, a single metal 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). Above all, from the viewpoint of versatility of conductor layer formation, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel-chromium alloy as an alloy , Copper / nickel alloy, copper / titanium alloy; 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 so as to function as a wiring layer, for example. At this time, the line (circuit width) / space (inter-circuit width) 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, The thickness 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 need not 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 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, depending on the design of the circuit board. In addition, when the insulating layer is polished or ground after the insulating layer is formed and the conductor layer is exposed to perform interlayer connection of the conductor layer, the conductor layer that performs interlayer connection and the conductor layer that does not perform interlayer connection have the thickness Are preferably different. Among the conductor layers, the thickness of the conductor layer (conductive pillar) having the greatest thickness 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 pattern formation described later. Moreover, the conductor layer connected between layers may be a convex type.

  For example, the conductive layer is a pattern dry process in which a dry film (photosensitive resist film) is laminated on a substrate, a pattern is formed by exposing and developing the dry film under predetermined conditions using a photomask. 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 the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used. For example, a dry film formed of a resin such as a novolac resin or an acrylic resin can be used. The lamination conditions of the base material and the dry film can be the same as those of the base material and the resin sheet to be described later. Peeling of the dry film can be performed using, for example, an alkaline peeling 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 substrate, the resin composition layer is preferably formed so that the conductor layer is embedded in the resin composition layer.

  Formation of a resin composition layer is performed by laminating | stacking a resin sheet and a base material, for example. This lamination can be performed, for example, by bonding the resin composition layer to the substrate by thermocompression bonding the resin sheet to the substrate from the support side. Examples of the member that heat-presses the resin sheet to the base material (hereinafter sometimes referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll, etc.). It is done. In addition, it is preferable not to press the thermocompression bonding member directly on 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 performed by, for example, a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C. The thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. In addition, you may perform lamination | stacking and a smoothing process continuously using a vacuum laminator.

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

  After forming the resin composition layer on the substrate, the resin composition layer is thermoset to form an insulating layer. Although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, 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 in the range of 170 ° C to 200 ° C. ), And 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).

  Prior to thermosetting the resin composition layer, the resin composition layer may be subjected to a preheating 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 to 120 ° C. (preferably 60 to 110 ° C., more preferably 70 to 100 ° C.). 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. The circuit board manufacturing method may further include an optional 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 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 grinder.

  The circuit board manufacturing method may include, for example, a step (3) of interconnecting conductor layers. In this step (3), a conductor layer provided on one side of the insulating layer (for example, a conductor layer formed on the substrate surface) 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. . In addition, the step (3) may include, for example, polishing or grinding the other side of the insulating layer to expose a conductor layer formed on one side of the insulating layer, thereby performing interlayer connection.

  When performing interlayer connection using via holes, for example, after forming a via hole in an insulating layer formed on a substrate with a wiring layer, a conductor layer is formed on the opposite side of the insulating layer from the substrate, and a correlation connection is made. I do. Examples of the method for forming the via hole include laser irradiation, etching, mechanical drilling, and the like. Among these, 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 laser, a YAG laser, or an excimer laser. For example, laser irradiation may be performed on the support side of the resin sheet to form a via hole that penetrates the support and the insulating layer and exposes the conductor layer on the substrate surface.

  Laser irradiation can be performed by an appropriate process according to the selected laser beam 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 outline 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 called a desmear process. For example, when the conductor layer is formed on the insulating layer by a plating process, wet desmear treatment may be performed on the via hole. In addition, when the conductor layer is formed on the insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Furthermore, a roughening process may be performed on the insulating layer by a desmear process.

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

  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 substrate are electrically connected, and interlayer connection is performed. Examples of the method for forming the conductor layer include a plating method, a sputtering method, a vapor deposition method, and the like, and among them, the plating method is 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. Moreover, when the support body in a resin sheet is metal foil, the conductor layer which has a desired wiring pattern can be formed by a subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Moreover, this conductor layer may have a single layer structure, or may have a multilayer structure including two or more layers of different kinds of materials.

  Here, the example of embodiment which forms a conductor layer on an insulating layer is demonstrated in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing 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 on the exposed plating seed layer by electrolytic plating. At this time, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by a process such as etching to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as the said dry film.

  The conductor layer may include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example. Moreover, the conductor layer may be comprised only from the electrode pad.

  The conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after the formation of 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 substrate with the wiring layer is polished or ground, and the conductor layer formed on the substrate is replaced with the insulating layer substrate. Expose to the opposite side. As the method for polishing and grinding the insulating layer, any method that can expose the conductor layer on the substrate surface can be used. Among them, a method in which a polished surface or a ground surface parallel to the layer plane of the insulating layer is obtained by polishing or cutting is preferable. Examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as buffing, and a surface grinding method by rotating a grindstone. In addition, when performing interlayer connection by polishing or grinding the insulating layer, the process of removing smear, roughening, and forming a conductor layer on the insulating layer is performed in the same manner as when performing interlayer connection using via holes. May be. Moreover, 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 circuit board manufacturing method may include, for example, a step (4) of removing the 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 substrate having a peelable first metal layer and a second metal layer is used. A preferred example will be described below. A conductor layer is formed on the surface of the second metal layer of the substrate having the first metal layer and the second metal layer. Furthermore, a resin composition layer is formed on the second metal layer so that the conductor layer is embedded in the resin composition layer, and is thermally cured to obtain an insulating layer. Then, after performing interlayer connection as needed, parts other than the 2nd metal layer of a base material are peeled. Then, the second metal layer is removed by etching with an etchant such as an aqueous copper chloride solution. Thereby, the substrate is removed. Under the present circumstances, you may remove a base material in the state which protected the conductor layer with the protective film as needed.

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

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

  As a bonding condition between the circuit board and the semiconductor chip, any condition that allows the conductor connection between the terminal electrode of the semiconductor chip and the circuit wiring of the circuit board can be adopted. For example, conditions used in flip chip mounting of a semiconductor chip can be adopted. Further, for example, the semiconductor chip and the circuit board may be bonded via an insulating adhesive.

  As an example of the bonding method, there is a method in which a semiconductor chip is pressure-bonded 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).

  Another example of the bonding method is a method in which a semiconductor chip is reflowed and bonded to a circuit board. Reflow conditions are good also as the range of 120 to 300 degreeC.

  After the semiconductor chip is bonded to the circuit board, the semiconductor chip may be filled with a mold underfill material. As the mold underfill material, the above-described resin composition may be used, or the above-described 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. As a semiconductor chip package according to the second embodiment, for example, a Fan-out type WLP can be cited.

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

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

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

  Examples of base materials include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); Examples include a substrate subjected to thermosetting treatment; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

  The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include “Riva Alpha” manufactured by Nitto Denko Corporation.

(Process (B))
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The 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 number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like. For example, the semiconductor chips may be aligned and temporarily fixed in a matrix of a plurality of rows and a plurality of columns.

(Process (C))
Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed by a 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 thermosetting the resin composition layer to form a sealing layer.

The resin composition layer is preferably formed by a compression molding method utilizing the excellent compression moldability of the resin composition. In the compression molding method, usually, a semiconductor chip and a resin composition are placed in a mold, and pressure and heat are applied to the resin composition in the mold to form a resin composition layer that covers the semiconductor chip.
The specific operation of the compression molding method can be performed as follows, for example. 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. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition to perform compression molding.
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. The resin composition is placed on the lower mold. Further, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped so that the resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

  The molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be adopted so that good sealing is achieved. For example, the mold temperature during 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, preferably 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 curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, particularly preferably 20 minutes or less. Usually, after the resin composition layer is formed, the mold is removed. The removal of the mold may be performed 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, the resin composition layer can be formed on the semiconductor chip by thermocompression bonding the resin composition layer of the resin sheet and the semiconductor chip. Lamination of the resin sheet and the semiconductor chip can be usually performed in the same manner as the lamination of the resin sheet and the base material in the circuit board manufacturing method using a semiconductor chip instead of the base material.

  After forming the resin composition layer on the semiconductor chip, the resin composition layer is thermally cured to obtain a sealing layer that covers the semiconductor chip. Thereby, the semiconductor chip is sealed with the cured product of the resin composition. The thermosetting conditions for the resin composition layer may be the same as the thermosetting conditions for the resin composition layer in the method for manufacturing a circuit board. Furthermore, before the resin composition layer is thermally cured, the resin composition layer may be subjected to a preheating treatment in which the resin composition layer is heated at a temperature lower than the curing temperature. The processing conditions for the preheating process may be the same as the preheating process in the circuit board manufacturing method.

(Process (D))
A process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip. As the peeling method, it is desirable to adopt an appropriate method according to the material of the temporarily fixed film. As a peeling method, the method of peeling by heating, foaming, or expanding a temporarily fixed film is mentioned, for example. Moreover, as a peeling method, the method of irradiating a temporarily fixed film with an ultraviolet-ray through a base material and reducing the adhesive force of a temporarily fixed film and peeling is mentioned, for example.

In the method in which the temporarily fixed film is peeled by heating, foaming or expanding, the heating condition is 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.

(Process (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 are peeled off.

  As the material for the rewiring layer, any material having an insulating property can be used. Among these, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easy manufacture of the semiconductor chip package. Moreover, you may use the resin composition of this invention as this thermosetting resin.

  After forming the rewiring layer, via holes may be formed in the rewiring layer in order to connect the semiconductor chip and the rewiring layer.

  In the method of forming a via hole when the material of the rewiring layer is a photosensitive resin, normally, the surface of the rewiring layer is irradiated with active energy rays through a mask pattern, and the rewiring layer in the irradiated portion is irradiated with light. Harden. Examples of active energy rays 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. As an exposure method, for example, a contact exposure method in which a mask pattern is brought into close contact with the rewiring formation layer and exposed, a non-contact exposure method in which the mask pattern is exposed using parallel rays without being brought into close contact with the rewiring formation layer, etc. Is mentioned.

  After the rewiring formation layer is photocured, the rewiring formation layer is developed, the unexposed portion is removed, and a via hole is formed. 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 a method for forming a via hole when the material of the rewiring forming layer is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Among these, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide 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, 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 formation layer.

(Process (F))
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method for forming the rewiring layer on the rewiring formation layer can be the same as the method for forming the conductor layer on the insulating layer in the method for manufacturing a circuit board. Alternatively, the step (E) and the step (F) may be repeated to build up the rewiring layer and the rewiring forming layer alternately (build up).

(Process (G))
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 insulating properties can be used. Among these, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of easy manufacture of the semiconductor chip package. Moreover, you may use the resin composition of this invention as a thermosetting resin.

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

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

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

[14. Semiconductor device]
Examples of the semiconductor device on which the above-described semiconductor chip package is mounted include, for example, electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (for example, , Various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like).

  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 amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified. Further, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[Measurement method of viscosity of epoxy resin]
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., 1 ° 34 ′ × R24 cone rotor). The measurement was performed 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 at 45 ° C., 5.5 Pa · s, 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 Co., Ltd.), acid anhydride curing agent ( "HNA-100" manufactured by Nippon Nippon Chemical Co., Ltd., 10 parts of acid anhydride equivalent 179), 3 parts of glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115), glycidylamine type epoxy resin (Mitsubishi Chemical) "630", Epoxy equivalent 95) 7 parts, bisphenol A type epoxy resin (DIC "EXA-850CRP", Epoxy 3 parts of cis equivalent 173) and 0.1 part of imidazole curing accelerator (“2E4MZ” manufactured by Shikoku Kasei Co., Ltd.) were mixed with a mixer to obtain a resin composition.

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

[Example 3]
Instead of 10 parts of acid anhydride curing agent (“HNA-100” manufactured by Shin Nippon Rika Co., Ltd.), 5 parts of liquid novolak type phenol curing agent (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 141) is used. It was.
Except for the above, the same operation as in Example 1 was performed 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, 2 parts of an aliphatic epoxy resin (“YED-216D” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 120) was used instead of 3 parts of a bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC).
Except for the above, the same operation as in Example 1 was performed to obtain a resin composition.

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

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

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

[Comparative Example 3]
A liquid polybutadiene epoxy resin (“JP-400” manufactured by Nippon Soda Co., Ltd.) was not used.
Further, instead of 10 parts of acid anhydride curing agent (“HNA-100” manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 179), a cresol novolac type curing agent (“KA-1160” manufactured by DIC Corporation, phenolic hydroxyl group equivalent) 117) 5 parts were used.
Furthermore, the amount of glycidylamine type epoxy resin (“EP-3980S” manufactured by ADEKA, epoxy equivalent 115) was changed from 3 parts to 5 parts.
Except for the above, the same operation as in Example 1 was performed to obtain a resin composition.

[Measurement of linear thermal expansion coefficient (CTE) of cured product of resin composition]
(Production of cured product for evaluation)
A polyethylene terephthalate film (“501010” manufactured by Lintec Corporation, thickness 38 μm, 240 mm square) having a release treatment on one side was prepared. A glass cloth base epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works Co., Ltd., thickness 0.7 mm, 255 mm square) is overlaid on the untreated surface of the polyethylene terephthalate film that has not been subjected to the release treatment. The four sides were fixed with a polyimide adhesive tape (width 10 mm). Thereby, the fixed PET film containing a polyethylene terephthalate film and a glass cloth base-material epoxy resin double-sided copper clad laminated board was obtained.

  Methyl ethyl ketone was added to the resin compositions produced in Examples and Comparative Examples for dilution, and the viscosity of the resin compositions was adjusted to 4000 mPa · s. In addition, as a support, a polyethylene terephthalate film (“Lumirror R80” manufactured by Toray Industries, Inc., having a thickness of 38 μm, a softening point, which has been subjected to a release treatment on the surface with an alkyd resin release agent (“AL-5” manufactured by Lintec) 130 ° C.). On this support, the resin composition whose viscosity was adjusted as described above was applied 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 including the support and the resin composition layer.

  Each resin sheet (resin composition layer thickness 100 μm) was cut into a 200 mm square. Using the batch type vacuum pressure laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.) The laminate was in contact with the center of the surface subjected to the mold release treatment to obtain a multilayer sample. The above-mentioned lamination was carried out by reducing the pressure for 30 seconds and adjusting the pressure to 13 hPa or less, followed by pressure bonding at a temperature of 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  Next, 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 thermally cure the resin composition layer. Thereafter, the multilayer sample was taken out in a room temperature atmosphere and the support was peeled off, and then placed in an oven at 190 ° C. and heated for 90 minutes to further thermally cure the resin composition layer. The obtained multilayer sample contained a cured product layer obtained by curing the resin composition layer, a polyethylene terephthalate film, and a glass cloth base epoxy resin double-sided copper-clad laminate in this order.

  After the thermosetting, the polyimide adhesive tape was peeled off, the glass cloth base epoxy resin double-sided copper-clad laminate was removed, and the polyethylene terephthalate film was peeled off to obtain a cured product of a sheet-like resin composition. The obtained cured product may be referred to as “evaluated 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. About this test piece, the thermomechanical analysis was performed with the tension | pulling load method using the thermomechanical analyzer ("Thermo Plus TMA8310" by Rigaku Corporation). Specifically, after the test piece was mounted on the thermomechanical analyzer, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In the second measurement, the linear thermal expansion coefficient (ppm / ° C.) in the plane direction in the range from 25 ° C. to 150 ° C. was calculated.

[Measurement of warpage]
The resin compositions produced in Examples and Comparative Examples were compression molded on a 12-inch silicon wafer using a compression molding apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) A resin composition layer having a thickness of 300 μm was formed. Thereafter, the resin composition layer was cured by heating at 180 ° C. for 90 minutes. This obtained the sample substrate containing a silicon wafer and the hardened | cured material layer of a resin composition.

  The amount of warpage when the sample substrate was heated and cooled in the order of 35 ° C., 260 ° C., and 35 ° C. was measured using a shadow moiré measuring device (“Thermoire AXP” manufactured by Akorometrix). The measurement was performed in accordance with JEITA EDX-7311-24 of the Japan Electronics and Information Technology Industries Association standard. Specifically, using a virtual plane calculated by the least square method of all data on the substrate surface in the measurement region as a reference plane, the difference between the minimum value and the maximum value in the vertical direction from the reference plane was determined as the amount of warpage. The amount of warpage was determined to be “◯” when less than 2 mm, and “×” when 2 mm or more.

[Evaluation of adhesion]
A heat release sheet (Thermal release tape; “Riva Alpha” manufactured by Nitto Denko Co., Ltd.), which has adhesiveness at normal temperature and can be easily peeled 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 the examples and comparative examples were placed on the thermal release sheet on which the silicon chip was placed, and the compression mold apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) A resin composition layer having a layer thickness of 500 μm embedded with a silicon chip was formed by compression molding. The heat release sheet and the silicon wafer were removed by heating at 180 ° C. so that the heat release sheet was peelable. Thereafter, the resin composition layer was heated at 180 ° C. for 90 minutes to thermally cure the resin composition layer. Thus, a resin wafer including a cured product layer of the resin composition and a silicon chip embedded in the cured product layer was obtained.

  Then, the thermal cycle test of the resin wafer was implemented. This thermal cycle test is a test in which cooling to −55 ° C. and heating to 125 ° C. are taken as one cycle and the cooling and heating are repeated 1000 cycles. The resin wafer was observed after the thermal cycle test, and the case where delamination occurred at the interface between the silicon chip and the cured product layer was determined as “X”, and the case where delamination did not occur was determined as “◯”. Further, when a crack occurred 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 apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) A resin composition layer having a thickness of 300 μm was formed. Thereafter, the resin composition layer is observed, and “○” indicates that the resin composition can be filled up to the edge of the wafer, “X” indicates that no filling has occurred, and cracks occur on the surface of the resin composition layer after compression molding. When it occurred, it was determined as a “crack”.

[Measurement method of dielectric loss tangent]
A compression molding apparatus (mold temperature: 130 ° C., pressure: 6 MPa, cure time: 10 minutes) is used for the resin compositions produced in the examples and comparative examples on a SUS plate whose surface has been subjected to a mold release treatment. The resin composition layer having a thickness of 300 μm was formed by compression molding. The SUS board was peeled off, and the resin composition layer was thermally 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 into a length of 80 mm and a width of 2 mm to obtain an evaluation sample for dielectric loss tangent measurement. With respect to this evaluation sample, the dielectric loss tangent 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 (“HP 8362B” manufactured by Agilent Technologies).

[result]
The results of the above-described examples and comparative examples are shown in the following table. In the following table, the meanings of the abbreviations are as follows.
JP400: 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.).
JP200: Polybutadiene epoxy resin (“JP-200” manufactured by Nippon Soda Co., Ltd., 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, epoxy equivalent 193, number average molecular weight Mn = 5900, viscosity 45 Pa · s at 45 ° C.).
HNA-100: An acid anhydride curing agent (“HNA-100” manufactured by Shin Nippon Chemical Co., Ltd., acid anhydride equivalent 179).
KA-1160: Cresol novolac type curing agent (“KA-1160” manufactured by DIC, phenolic hydroxyl group equivalent 117).
MEH-8000H: Liquid novolac 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, epoxy equivalent 115). Liquid YED-216D: aliphatic epoxy resin (“YED-216D” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 120). Liquid 630: Glycidylamine 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, 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).

[Consideration]
As can be seen from Table 1, the resin compositions according to the examples are excellent in compression moldability. Moreover, the hardened | cured material of the resin composition which concerns on an Example has a low linear thermal expansion coefficient, can suppress curvature, and is excellent in high adhesiveness even if it repeats a heating and cooling. Therefore, according to the present invention, a resin composition layer that has a low coefficient of linear thermal expansion, can suppress warping, can obtain a cured product that can obtain high adhesion even after repeated heating and cooling, and is excellent in compression moldability. It was confirmed that can be realized.
Moreover, according to the resin composition of the present invention using an epoxy resin having an alkene skeleton in the molecule, by comparing Comparative Example 3 and the example without using an epoxy resin having an alkene skeleton in the molecule, In general, it was confirmed that a cured product having a low dielectric loss tangent was obtained.
Moreover, in Examples 1-5, even if it is a case where it does not contain (D) component-(E) component, although it is different in a grade, it has confirmed that it results in the same result as the said Example. .

DESCRIPTION OF SYMBOLS 100 Semiconductor chip package 110 Semiconductor chip 120 Sealing layer 130 Rewiring formation layer 140 Rewiring layer 150 Solder resist layer 160 Bump

Claims (14)

(A) an epoxy resin having a viscosity of 20 Pa · s or less at 45 ° C. and having an alkene skeleton in the molecule;
A resin composition comprising (B) an inorganic filler, and (C) a curing agent.   The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure in the molecule.   The resin composition according to claim 1 or 2, wherein the component (A) has a viscosity of 15 Pa · s or less at 45 ° C.   (A) Resin composition as described in any one of Claims 1-3 whose content of a component is 0.2 mass%-10 mass% with respect to 100 mass% of non-volatile components of a resin composition. .   (B) The resin composition as described in any one of Claims 1-4 whose average particle diameter of a component is 0.1 micrometer-10 micrometers.   (C) The resin composition as described in any one of Claims 1-5 whose component is an acid anhydride type hardening | curing agent or a phenol type hardening | curing agent.   Furthermore, the resin composition as described in any one of Claims 1-6 containing (D) epoxy resins other than (A) component.   Furthermore, the resin composition as described in any one of Claims 1-7 containing (E) hardening accelerator.   The resin composition as described in any one of Claims 1-8 which is a resin composition for semiconductor sealing or an insulating layer.   The resin composition according to any one of claims 1 to 9, which is a liquid resin composition.   The resin sheet which has a support body and the resin composition layer containing the resin composition of any one of Claims 1-10 provided on this support body.   The circuit board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-10.   A semiconductor chip package comprising the circuit board according to claim 12 and a semiconductor chip mounted on the circuit board.   The semiconductor chip package containing a semiconductor chip and the hardened | cured material of the resin composition as described in any one of Claims 1-10 which seals the said semiconductor chip.

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