KR20240066145A - Resin composition - Google Patents

Abstract

[Problem] To provide a resin composition that has a low linear thermal expansion coefficient, can suppress warping, can obtain a cured product that achieves high adhesion even after repeated heating and cooling, and has excellent compression moldability.
[Solution] 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.

Description

Resin composition {RESIN COMPOSITION}

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

Recently, the demand for small, high-performance electronic devices such as smartphones and tablet-type devices is increasing, and accordingly, the insulating layer for the semiconductor chip package used in these small electronic devices is also required to have additional high functionality. As such an insulating layer, for example, those formed by curing a resin composition are known (see, for example, Patent Documents 1 and 2).

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

The insulating layer is required to have a low dielectric loss tangent in order to reduce electrical signal loss. Therefore, as a result of examination, the present inventor discovered that an insulating layer with 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 investigation by the present inventor, it was found that a resin composition containing an epoxy resin having an alkene skeleton in the molecule has low compression moldability. For a resin composition with low compression moldability, it is difficult to fill every nook and cranny with the resin composition when attempting to form a resin composition layer by a compression molding method.

Additionally, in recent years, smaller semiconductor chip packages have been required, and therefore, the insulating layer used in the semiconductor chip package has been required to be thinner. For this reason, there is a demand for the development of an insulating layer that has a low coefficient of linear thermal expansion (CTE, sometimes referred to as coefficient of thermal expansion) and is capable of suppressing warping. In addition, the insulating layer is required to have high adhesion even after repeated heating and cooling. For example, the insulating layer in close contact with the silicon chip is required to be difficult to peel off from the silicon chip even after repeated heating and cooling. However, the conventional resin composition containing an epoxy resin having an alkene skeleton in the molecule did not achieve satisfactory performance in evaluation of linear thermal expansion coefficient, bending, and adhesion.

The resin composition used to form the insulating layer can also be considered to 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 that seals the semiconductor chip in a semiconductor chip package. The above-mentioned problems also occur even when the resin composition is used as a sealing material for a semiconductor chip package.

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

As a result of intensive studies to solve the above problems, the present inventor has found (A) an epoxy resin having a viscosity in a predetermined range at 45°C and having an alkene skeleton in the molecule, (B) an inorganic filler, and (C) It was discovered that the above problems could be solved by a resin composition containing a combination of curing agents, and the present invention was completed.

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,

(B) inorganic filler, and

(C) A resin composition containing 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 resin composition according to any one of [1] to [3], wherein the content of component (A) is 0.2% by mass to 10% by mass based on 100% by mass of non-volatile components of the resin composition.

[5] The resin composition according to any one of [1] to [4], wherein the average particle diameter of the component (B) is 0.1 μm to 10 μm.

[6] The resin composition according to any one of [1] to [5], wherein the (C) component is an acid anhydride-based curing agent or a phenol-based curing agent.

[7] The resin composition according to any one of [1] to [6], further comprising an epoxy resin (D) other than 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 sealing or insulating layers.

[10] The resin composition according to any one of [1] to [9], which is a liquid resin composition.

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

[12] A circuit board comprising an insulating layer formed by 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] for sealing the semiconductor chip.

According to the present invention, it is possible to obtain a cured product that has a low linear thermal expansion coefficient, can suppress warping, and has high adhesion even after repeated heating and cooling, and is also excellent in compression moldability; A resin sheet having a resin composition layer containing the above resin composition; A circuit board including an insulating layer formed by a cured product of the above resin composition; And, a semiconductor chip package including a cured product of the above resin composition; can be provided.

[Figure 1] Figure 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, embodiments and examples will be shown and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with any modification without departing from the scope of the claims and equivalents of the present invention.

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

[One. Overview of resin composition]

The resin composition of the present invention includes (A) an epoxy resin having a viscosity in a predetermined range at 45°C and having an alkene skeleton in the molecule, (B) an inorganic filler, and (C) a curing agent. In the following description, the “epoxy resin that has a viscosity in a predetermined range at 45°C and has an alkene skeleton in the molecule” as component (A) may be referred to as “(A) epoxy resin.”

By containing the above-mentioned component (A), component (B), and component (C) in combination, the resin composition has excellent compression moldability, has a low linear thermal expansion coefficient, can suppress warping, and has excellent heating and cooling properties. Even if the process is repeated, the desired effect of the present invention can be obtained in that a cured product capable of exhibiting high adhesion is obtained. The cured product of this resin composition can be suitably used as an insulating layer and sealant of a semiconductor chip package, taking advantage of its excellent properties.

In addition, the above resin composition may further contain an arbitrary component in combination with component (A), component (B), and component (C). Optional components include, for example, (D) epoxy resins other than (A) epoxy resins, (E) curing accelerators, etc.

[2. (A) Epoxy]

(A) The epoxy resin has a viscosity within a predetermined range 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 this viscosity, the compression moldability of the resin composition can be improved. Furthermore, by using the (A) epoxy resin of this viscosity, a cured product can be obtained that has a low coefficient of linear thermal expansion, can suppress warping, and can exhibit high adhesion even after repeated heating and cooling. (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, or 3 Pa·s or more.

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

Additionally, (A) the epoxy resin has an alkene skeleton in the molecule. Here, the alkene skeleton represents a structure represented by the following formula (1). The number of bonds to the carbon atom shown in the formula (1) is not limited to the preceding atom to which it is bonded, but is usually a hydrogen atom or a carbon atom. By using the (A) epoxy resin having an alkene skeleton in this way, the dielectric loss tangent of the cured product of the resin composition can usually be lowered. Additionally, it is usually possible to improve the insulation of the cured product or lower the hygroscopicity.

Chemical formula (1)

(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, or may have an alkene skeleton in both the main chain and the side chain of the molecule. Among these, from the viewpoint of significantly obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product, it is preferable that the molecule has an alkene skeleton in the side chain.

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

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

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

Preferred examples of the above structural units having an alkene skeleton include structural units shown in the following formula (2) or (3). The structural unit represented by the formula (2) and the structural unit represented by the formula (3) can both 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. Additionally, 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 significantly obtaining the desired effect of the present invention and effectively lowering the dielectric loss tangent of the cured product.

Chemical formula (2)

Chemical formula (3)

(A) The number of the above structural units having an alkene skeleton contained in the epoxy resin molecule may be one or two or more. From the viewpoint of significantly obtaining the desired effect of the present invention and effectively lowering the dielectric loss tangent of the cured product, (A) the epoxy resin contains two or more of the above structural units having an alkene skeleton as repeating units in the molecule. It is desirable.

In particular, the (A) epoxy resin preferably has a polybutadiene structure in the molecule from the viewpoint of significantly obtaining the desired effect of the present invention and effectively lowering the dielectric loss tangent of the cured product. Polybutadiene structure refers to a structure that can be formed by polymerizing butadiene. Specific examples of polybutadiene structures include structures containing two or more structural units selected from the structural units represented by the formula (2) and the structural units represented by the formula (3) in one molecule. Among these, it is preferable that the (A) epoxy resin contains two or more structural units represented by the general formula (2) in one molecule.

In addition, it is preferable that the number of structural units represented by the formula (2) per molecule of the epoxy resin (A) is greater than the number of structural units represented by the formula (3). As a result, the desired effect of the present invention can be significantly achieved, and in particular, the compression moldability of the resin composition can be effectively improved, and the adhesion of the cured product when heating and cooling is repeated can be effectively improved.

Additionally, (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, or may have epoxy groups in both the main chain and side chain of the molecule. Among these, from the viewpoint of significantly obtaining the desired effect of the present invention and from the viewpoint of effectively lowering the dielectric loss tangent of the cured product, it is preferable to have an epoxy group in the side chain of the molecule.

(A) The epoxy resin may have an epoxy group in the above structural unit having an alkene skeleton. However, from the viewpoint of significantly obtaining the desired effect of the present invention and effectively lowering the dielectric loss tangent of the cured product, the above having an alkene skeleton may be used. It is preferable to have an epoxy group in a structural unit different from the structural unit of.

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

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

Chemical formula (4)

Chemical formula (5)

Additionally, it is preferable that the number of structural units represented by the formula (4) per molecule of the (A) epoxy resin is greater than the number of structural units represented by the formula (5). As a result, the desired effect of the present invention can be significantly achieved, and in particular, the compression moldability of the resin composition can be effectively improved, and the adhesion of the cured product when heating and cooling is repeated can be effectively improved.

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

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

Chemical formula (6)

(A) Specific examples of the epoxy resin include “JP400” manufactured by Nippon Soda Co., Ltd., which has a molecular structure represented by the above general formula (6). In addition, (A) component may be used individually, or two or more types may be used in combination at an arbitrary ratio.

In general, epoxy resins are divided into liquid epoxy resins at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20°C (sometimes referred to as “solid epoxy resins”). .). (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 improved, and the adhesion of the cured product when heating and cooling are repeated can be effectively improved.

(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, especially preferably It is less than 4000. (A) When the number average molecular weight (Mn) of the epoxy resin is more than the lower limit of the above range, the compression moldability of the resin composition is particularly improved, the linear thermal expansion coefficient of the cured product of the resin composition is effectively lowered, or the cured product suppresses warping. The ability can be effectively increased, and peeling of the cured product due to heating and cooling can be effectively suppressed. In addition, (A) when the number average molecular weight (Mn) of the epoxy resin is below the upper limit of the above range, the compression moldability of the resin composition is particularly improved, the linear thermal expansion coefficient of the cured product of the resin composition is effectively lowered, or the resin composition is improved. By increasing the toughness of the hardened product, the occurrence of cracks can be effectively suppressed.

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

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

(A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and even more preferably 110 to 1000. (A) When the epoxy equivalent weight of the epoxy resin is within the above range, the crosslinking density of the cured product of the 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 group. 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, particularly preferably -70°C or higher. (A) When the epoxy resin has a glass transition temperature in the above range, the desired effect of the present invention can be significantly achieved.

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

[3. (B) Inorganic filler]

The resin composition contains an inorganic filler as component (B). (B) By using an inorganic filler, the coefficient of linear thermal expansion of the cured product of the resin composition can be reduced and warping can be suppressed.

(B) As the material for the inorganic filler, an inorganic compound is used. (B) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, 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, Examples include barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable from the viewpoint of significantly obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. (B) Inorganic fillers may be used individually, or two or more types may be used in combination in any ratio.

Usually, the (B) inorganic filler is contained in the resin composition in the form of particles. (B) The average particle diameter 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 the inorganic filler is within the above range, the desired effect of the present invention can be significantly achieved. In particular, when the average particle diameter of the inorganic filler (B) is below the upper limit of the above range, the compression moldability of the resin composition can be effectively improved and flow marks can be reduced. Additionally, the adhesion of the cured product can be effectively increased when heating and cooling are repeated. In addition, when the average particle diameter of the inorganic filler (B) is within the above range, the surface roughness of the insulating layer can usually be lowered when the insulating layer is formed with a cured resin composition.

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

Examples of the above (B) inorganic fillers include “MSS-6” and “AC-5V” manufactured by Tatsumori Corporation; “SP60-05” and “SP507-05” manufactured by Shin-Ni-Tetsu Sumikin Materials, Inc.; “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C” manufactured by Adomatex Corporation; “UFP-30”, “SFP-130MC”, “FB-7SDC”, “FB-5SDC”, and “FB-3SDC” manufactured by Denka Corporation; “Actual writing NSS-3N”, “Actual writing NSS-4N”, and “Actual writing NSS-5N” manufactured by Tokuyama Corporation; Examples include "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "FE9" manufactured by Adomatex Corporation.

(B) The inorganic filler is preferably surface treated with an appropriate surface treatment agent. By surface treatment, the moisture resistance and dispersibility of the (B) inorganic filler can be improved. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercapto coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned.

Commercially available surface treatment agents include, for example, "KBM22" (dimethyldimethoxysilane), manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd. “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Kaku Kogyoso, “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Kogyoso, “KBM573” (N -Phenyl-3-aminopropyltrimethoxysilane), “KBM5783” (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyo, “SZ-31” (HEXA) manufactured by Shin-Etsu Chemical methyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd., and "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Kogyo Co., Ltd. Among them, 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 more preferable, and N-phenyl-3- Aminopropyltrimethoxysilane and N-phenyl-3-aminooctyltrimethoxysilane are more preferred. In addition, one type of surface treatment agent may be used individually, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of (B) the inorganic filler. (B) The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, especially preferably, from the viewpoint of improving the dispersibility of the inorganic filler (B). It is more than 0.2mg/㎡. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in sheet form, the carbon amount is preferably 1 mg/m2 or less, more preferably 0.8 mg/m2 or less, especially preferably It is less than 0.5mg/㎡.

The amount of carbon per unit surface area of the (B) inorganic filler is determined by washing the (B) inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). After doing this, it can be measured. Specifically, a sufficient amount of methyl ethyl ketone and the inorganic filler (B) surface-treated with a surface treatment agent are mixed and ultrasonic cleaned at 25°C for 5 minutes. Thereafter, the supernatant is removed, the solid content is dried, and then the amount of carbon per unit surface area of the (B) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, “EMIA-320V” manufactured by Horiba Sesakusho Co., Ltd. can be used.

The amount of the inorganic filler (B) 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 or more, based on 100% by mass of the non-volatile component in the resin composition. Moreover, it is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 86 mass% or less. (B) When the amount of the inorganic filler is within the above range, the desired effect of the present invention can be significantly achieved, and in particular, the coefficient of linear thermal expansion of the resin composition can be effectively lowered.

[4. (C) Hardener]

The resin composition contains a curing agent as component (C). The (C) curing agent usually has the function of curing the resin composition by reacting with an epoxy resin such as (A) epoxy resin and (D) epoxy resin. (C) One type of hardening agent may be used individually, or two or more types may be used in combination in an arbitrary ratio.

(C) As the curing agent, a compound capable of curing the resin composition by reacting with the epoxy resin can be used, for example, acid anhydride curing agent, phenol curing agent, activated ester curing agent, cyanate ester curing agent, benzox. Photo-based curing agents, carbodiimide-based curing agents, etc. can be mentioned. Among them, from the viewpoint of significantly obtaining the effects of the present invention, acid anhydride-based curing agents and phenol-based curing agents are preferable.

Examples of the acid anhydride-based curing agent include those 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 anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride. , Bensophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a ,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis( Anhydrotrimellitate) and polymer-type acid anhydrides such as styrene/maleic acid resin, which is a copolymerization of styrene and maleic acid.

Examples of the phenol-based curing agent include those having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) per molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferable. Additionally, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferable. 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 phenol novolak curing agent containing a triazine skeleton is preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include “MEH-7700,” “MEH-7810,” “MEH-7851,” and “MEH-8000H” manufactured by Meiwa Kasei Co., Ltd.; “NHN,” “CBN,” and “GPH” manufactured by Nihon Kayaku Co., Ltd.; “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-495V” manufactured by Shin-Ni-Tetsu Sumikin Kagaku, 「SN-375」, 「SN-395」; “TD-2090”, “TD-2090-60M”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018”, “LA-3018-50P” manufactured by DIC, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, “KA-1165”; Examples include “GDP-6115L,” “GDP-6115H,” and “ELPC75” manufactured by Gunei Chemical Co., Ltd.

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

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

Phenol compounds or naphthol compounds include, for example, hydroquinone, resorcinol, 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, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred 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 novolak, and an active ester compound containing a phenol novolac. and active ester compounds containing benzoylides. Among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as “EXB9451,” “EXB9460,” “EXB9460S,” “HPC-8000,” “HPC-8000H,” and “HPC.” -8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); As an active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC); As an active ester compound containing an acetyl compound of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); As an active ester compound containing the benzoylate of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); As an active ester-based curing agent that is an acetylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation); Examples of active ester curing agents that are benzoylates of phenol novolak include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); etc. can be mentioned.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6-dimethyl. phenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate) Natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether; Polyfunctional cyanate resins derived from phenol novolac, cresol novolac, etc.; Prepolymers in which some of these cyanate resins are triazined; etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolak-type polyfunctional cyanate ester resins); “ULL-950S” (polyfunctional cyanate ester resin); “BA230”, “BA230S75” (prepolymer in which part or all of bisphenol A dicyanate is triazine to form a trimer); etc. can be mentioned.

Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Kobunshi Co., Ltd., and “P-d” and “F-a” manufactured by Shikoku Kaseikogyo Co., Ltd.

Specific examples of carbodiimide-based curing agents include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

The content of 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 significantly obtaining the desired effect of the present invention. is 10 mass% or more, preferably 70 mass% or less, more preferably 65 mass% or less, and even more preferably 60 mass% or less.

When the number of epoxy groups in the epoxy resin containing the (A) epoxy resin and (D) the epoxy resin is 1, the number of active groups in the curing agent (C) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably is 0.3 or more, preferably 2 or less, more preferably 1.8 or less, further preferably 1.6 or less, particularly preferably 1.4 or less. Here, the “number of epoxy groups in the epoxy resin” is the sum of the mass of the non-volatile component of the epoxy resin present in the resin composition divided by the epoxy equivalent. In addition, “the number of active groups of the (C) curing agent” is the sum of the mass of the non-volatile component of the (C) curing agent present in the resin composition divided by the active group equivalent. When the number of active groups in the curing agent (C) is within the above range when the number of epoxy groups in the epoxy resin is 1, the desired effect of the present invention can be significantly obtained, and the heat resistance of the cured product of the resin composition layer is usually further improved. .

[5. (D) optional epoxy resin]

The resin composition may contain (D) epoxy resin other than the (A) epoxy resin described above as an optional component.

(D) As the epoxy resin, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris. Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak 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 with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin , cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. Epoxy resins may be used individually, or two or more types may be used in combination.

The resin composition preferably contains (D) an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the non-volatile component of the epoxy resin (D) is preferably 50% by mass or more. Preferably it is 60 mass% or more, especially preferably 70 mass% or more.

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

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

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, and phenol novolac type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, aliphatic epoxy resins, and epoxy resins having a butadiene structure are preferable, and bisphenol A-type epoxy resins and glycidylamine-type epoxy resins are preferred. Epoxy resins and aliphatic epoxy resins are more preferred.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; “EXA-850CRP” (bisphenol A type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epicoat 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER807” and “1750” (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630” and “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YED-216D” manufactured by Mitsubishi Chemical Corporation (aliphatic epoxy resin); “ZX1059” manufactured by Nippon Tetsu Sumikin Chemical Co., Ltd. (mixture of bisphenol 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-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Celoxide 2021P” manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); “PB-3600” manufactured by Daicel Corporation (epoxy resin with a butadiene structure); “EP-3980S” manufactured by ADEKA (glycidylamine type epoxy resin); “ELM-100H” manufactured by Tsumitomo Chemical Co., Ltd. (glycidylamine type epoxy resin); etc. can be mentioned. These may be used individually or in combination of two or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable.

As solid epoxy resins, non-xylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, Phenyl 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 preferred, 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 Corporation; “HP-4700” and “HP-4710” (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; “HP-7200” (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; “HP-7200HH”, “HP-7200H”, “EXA-7311”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” manufactured by DIC Corporation ( naphthylene ether type epoxy resin); “EPPN-502H” manufactured by Nihon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy resin) manufactured by Nihon Kayaku Co., Ltd.; “ESN475V” (naphthalene-type epoxy resin) manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.; "ESN485" (naphthol novolac type epoxy resin) manufactured by Shin-Ni-Tetsu Sumikin Chemical Co., Ltd.; "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YX4000HK” manufactured by Mitsubishi Chemical Corporation (bixylenol type epoxy resin); “YX8800” manufactured by Mitsubishi Chemical Corporation (anthracene type epoxy resin); “PG-100” and “CG-500” manufactured by Osaka Gas Chemical Co., Ltd.; “YL7760” manufactured by Mitsubishi Chemical Corporation (bisphenol AF type epoxy resin); "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER1010” manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin); and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

(D) When using a combination of liquid epoxy resin and solid epoxy resin as the epoxy resin, the ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:15 in mass ratio, more preferably 1:0.1 to 1:15. is 1:0.3 to 1:10, particularly preferably 1:0.6 to 1:8. By keeping the amount ratio of the liquid epoxy resin and the solid epoxy resin within this range, appropriate adhesiveness is usually achieved when used in the form of a resin sheet. Additionally, usually, when used in the form of a resin sheet, sufficient flexibility is obtained and handleability is improved. Additionally, a cured product having sufficient breaking strength can usually be obtained.

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

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

When the resin composition contains an epoxy resin (D), the amount of the epoxy resin (D) is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, based on 100 parts by mass of the epoxy resin (A). Preferably it is 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 significantly achieved.

When the resin composition contains the (D) epoxy resin, the amount of the (D) epoxy resin is preferably 0.3% by mass or more, more preferably 0.5% by mass, when the non-volatile component in the resin composition is 100% by mass. More preferably, it is 0.7 mass% or more, and is also preferably 20 mass% or less, more preferably 16 mass% or less, and even more preferably 14 mass% or less. (D) By keeping the amount of epoxy resin within the above range, the mechanical strength and insulation reliability of the cured product of the resin composition can be improved.

[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 promoted when curing the resin composition.

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

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. are mentioned. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole , 1-Cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimida Zolyl-(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 Among them, imidazole compounds such as chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, include 2-ethyl-4-methylimidazole. 1-Benzyl-2-phenylimidazole is preferred.

As an imidazole-type hardening accelerator, a commercial item may be used, for example, "P200-H50" by Mitsubishi Chemical Corporation; “2E4MZ” manufactured by Shikoku Kasei Corporation; etc. can be mentioned.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene are preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organic metal complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes, organic iron 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 organometallic salts 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 the (E) curing accelerator is 0.01% by mass to 3% by mass based on 100% by mass of the resin component of the resin composition from the viewpoint of significantly obtaining the desired effect of the present invention. is preferable, 0.03 mass% to 1.5 mass% is more preferable, and 0.05 mass% to 1 mass% is further preferable.

[7. (F) optional additives]

In addition to the components mentioned above, the resin composition may further contain optional additives as optional components. Such additives include, for example, organic fillers; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thermoplastic resin; thickener; antifoaming agent; leveling agent; Adhesion imparting agent; coloring agent; flame retardants; Resin additives such as these can be mentioned. These additives may be used individually, or two or more types may be used in combination at any ratio.

Although the above-mentioned resin composition may contain a solvent as needed, it is preferable that it is a solvent-free resin composition that does not contain a solvent. In this way, even if it does not contain a solvent, the above-described resin composition containing the epoxy resin (A) can be fluidized when molded 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]

The resin composition can be manufactured, for example, by a method of stirring the blended components using a stirring device such as a rotary mixer.

[9. Characteristics of resin composition]

The above-mentioned resin composition has excellent compression moldability. Therefore, when forming a resin composition layer on a circuit board or semiconductor chip by compression molding, it is possible to fill every nook and cranny with the resin composition. Therefore, by curing the above resin composition layer, an insulating layer with excellent insulation reliability and a sealing layer with 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 mold device (mold temperature: 130° C., mold pressure: 6 MPa, cure time: 10 minutes) to produce a resin composition with a thickness of 300 μm. forms a layer. In this case, the resin composition can usually be filled up to the edge of the wafer while suppressing the occurrence of cracks.

In addition, according to the above-mentioned resin composition, a cured product with a low linear thermal expansion coefficient can be obtained. Therefore, by using this resin composition, an insulating layer and a sealing layer with a low linear thermal expansion coefficient can be obtained.

For example, using the above-mentioned resin composition, a cured product for evaluation is produced by the method described in the Examples, and the coefficient of linear thermal expansion of the cured product for evaluation is measured. In this case, the obtained linear thermal expansion coefficient is usually 10 ppm/°C or lower, preferably 9 ppm/°C or lower, and more preferably 8 ppm/°C or lower. There is no particular limitation on the lower limit, and is usually 0 ppm/°C, preferably 1 ppm/°C or more.

In addition, according to the above-described resin composition, it is possible to obtain a layer of cured material capable of suppressing warping. Therefore, by using this resin composition, an insulating layer and a sealing layer capable of suppressing warping of a circuit board and a semiconductor chip package can be obtained.

For example, using the above-described resin composition, a cured layer of the resin composition is formed on a 12-inch silicon wafer by the method described in the Examples to produce a sample substrate. In this case, when the sample substrate is heated and cooled at 35°C, 260°C, and 35°C in that order, the amount of warpage measured by the method described in the examples can usually be less than 2 mm.

Furthermore, according to the above-described resin composition, a cured product that can exhibit high adhesion even after repeated heating and cooling can be obtained. Therefore, by using this resin composition, it is possible to obtain an insulating layer or sealing layer that is unlikely to peel off due to temperature changes.

For example, a resin wafer containing a cured layer of a resin composition and a silicon chip embedded in the cured layer is manufactured by the method described in the Examples. When a thermal cycle test is performed on this resin wafer by the method described in the examples, the occurrence of delamination at the interface between the silicon chip and the cured material layer can usually be suppressed.

The present inventor estimates the structure in which the above excellent advantages are obtained by the resin composition of the present invention as follows. However, the technical scope of the present invention is not limited by the structure described below.

Since the above-mentioned resin composition contains the low-viscosity (A) epoxy resin, it has excellent fluidity during compression molding. Therefore, the resin composition can easily enter small gaps, thereby achieving excellent compression moldability.

Additionally, the inorganic filler (B) contained in the resin composition has a smaller degree of expansion and contraction due to temperature changes compared to the resin component. Additionally, since the (A) epoxy resin can function as a flexible plasticizing component after curing of the resin composition, it can absorb volume changes due to temperature changes. Therefore, the coefficient of linear thermal expansion of the cured product of the resin composition can be lowered.

Additionally, as described above, since the degree of expansion and contraction of the inorganic filler (B) due to temperature change is small, even if a temperature change occurs, the stress caused by the temperature change can be reduced. Additionally, since the (A) epoxy resin can function as a flexible plastic component after curing of the resin composition, even if stress occurs in the cured product, the (A) epoxy resin can absorb the stress. Therefore, since the generation of stress that may cause bending can be suppressed, bending can be suppressed.

Additionally, since the resin composition has excellent fluidity as described above, residual stress is unlikely to remain after molding the resin composition. Additionally, even if stress occurs due to temperature change, the epoxy resin (A) can absorb the stress as described above. Therefore, stress concentration is suppressed in the cured product of the resin composition. Therefore, even if heating and cooling are repeated, destruction due to temperature changes is unlikely to occur in the cured product of the resin composition, so the occurrence of delamination due to resin destruction can be suppressed.

Usually, the cured product of the above resin composition has a low dielectric loss tangent. Therefore, by using this resin composition, an insulating layer with a low dielectric loss tangent can be obtained.

For example, a cured layer of the resin composition is produced by the method described in the Examples. The dielectric loss tangent measured by the measurement method described in the examples for this cured layer is preferably 0.007 or less, more preferably 0.006 or less. The lower the lower limit of the dielectric loss tangent value, the more preferable it is, for example, it may be 0.001 or more.

The above resin composition may be in a liquid state or a solid state, but is preferably in a liquid state at the time of molding. For example, a resin composition that is liquid at room temperature (e.g., 20°C) may be molded by compression molding at room temperature without performing any special temperature adjustment, or may be heated to an appropriate temperature and molded by compression molding. Molding may be performed. In addition, a resin composition that is solid at room temperature can usually be changed to a liquid state by adjusting its temperature to a higher temperature (for example, 130°C), so it can be molded by compression molding by adjusting the temperature appropriately, such as heating. do. The above resin composition can usually become liquid at an appropriate temperature even without containing a solvent, and can be used, for example, as a liquid sealant.

[10. [Use of resin composition]

Taking advantage of the above-mentioned advantages, a sealing layer and an insulating layer can be formed with the cured product of the above resin composition. Therefore, this resin composition can be used as a resin composition for semiconductor sealing or insulating layers.

For example, the above resin composition is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), and an insulating layer of a circuit board (including a printed wiring board). It can be suitably used as a resin composition for forming (a resin composition for an insulating layer of a circuit board). In addition, for example, the above resin composition is a resin composition for forming the insulating layer (forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. It can be suitably used as a resin composition for use.

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

Semiconductor chip packages to which a sealing layer or an insulating layer formed from a cured product of the above resin composition can be applied include, 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 Lavel Package), and fan-doll PLP.

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

In addition, the above resin composition can be used in a wide range of applications where resin compositions are used, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, die bonding materials, hole filling resins, and component filling resins.

[11. [Resin sheet]

The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of a resin composition.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. It is less than ㎛. The lower limit of the thickness of the resin composition layer is not particularly limited and may be, for example, 1 μm or more, 5 μm or more, or 10 μm or more.

Examples of the support include films, metal foils, and release papers made of plastic materials, and film metal foils made of plastic materials are preferable.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”) .) polyester, etc.; Polycarbonate (hereinafter sometimes abbreviated as “PC”); Acrylic polymers such as polymethyl methacrylate (hereinafter sometimes abbreviated as “PMMA”); Cyclic polyolefin; Triacetylcellulose (hereinafter sometimes abbreviated as “TAC”); Polyether sulfide (hereinafter sometimes abbreviated as “PES”); polyether ketone; polyimide; etc. can be mentioned. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

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

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer.

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. Examples of commercially available release agents include "SK-1", "AL-5", and "AL-7" manufactured by Lintec, which are alkyd resin-based release agents. Moreover, as a support body with a release layer, for example, "Lumirror T60" manufactured by Torres; “Purex” manufactured by Teijin Corporation; Examples include “Unifill” manufactured by Unichika Co., Ltd.

The thickness of the support is preferably in the range of 5 μm to 75 μm, and 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 entire thickness of the support body with a release layer is within the above range.

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

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; Acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; Amide-based solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone; etc. can be mentioned. Organic solvents may be used individually, or two or more types may be used in combination in any ratio.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are such that the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it also varies 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 an organic solvent, the resin composition is dried at 50°C to 150°C for 3 to 10 minutes. Layers can be formed.

The resin sheet may, if necessary, contain any layers other than the support and the resin composition layer. For example, in the resin sheet, a protective film similar to the support may be provided on the side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is, for example, 1 μm to 40 μm. The protective film can prevent adhesion of dust or the like to the surface of the resin composition layer and scratches. When the resin sheet has a protective film, the resin sheet becomes usable by peeling off the protective film. Additionally, the resin sheet can be wound into a roll and stored.

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

Additionally, the resin sheet can be suitably used to seal semiconductor chips (resin sheet for semiconductor chip sealing). Applicable semiconductor chip packages include, for example, fan-out type WLP, fan-puppet WLP, fan-out type PLP, fan-puppet PLP, etc.

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

Additionally, resin sheets can be used in a wide range of other applications requiring high insulation reliability. For example, a resin sheet can be suitably used to form 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 from a cured product of the resin composition of the present invention. This circuit board can be manufactured, for example, by a manufacturing method including the following steps (1) and (2).

(1) A process of forming a resin composition layer on a substrate.

(2) A process of thermosetting the resin composition layer to form an insulating layer.

In step (1), the substrate is prepared. Examples of substrates include glass epoxy substrates, metal substrates (stainless steel, cold rolled steel (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. there is. Additionally, the base material may have a metal layer such as copper foil on the surface as a part of the base material. For example, a base material having a peelable first metal layer and a second metal layer on both surfaces may be used. When using such a substrate, a conductor layer as a wiring layer that can function as a circuit wiring is usually formed on the side of the second metal layer opposite to the first metal layer. Examples of the substrate having such a metal layer include "Micro Thin", an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Kinzoku Kogyo Co., Ltd.

Additionally, a conductor layer may be formed on one or both surfaces of the substrate. In the following description, a member including a base material and a conductor layer formed on the surface of the base material may be appropriately referred to as a “substrate with a wiring layer.” The conductor material included in the conductor 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. Materials containing the above metals can be mentioned. As the conductor material, a simple 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). Among them, from the viewpoint of versatility in forming the conductor layer, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; And, as alloys, alloys of nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy are preferable. Among them, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; And nickel-chromium alloy is more preferable, and the simple metal of copper is especially preferable.

The conductor layer may be pattern-processed to function as a wiring layer, for example. At this time, the line (circuit width)/space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20/20 ㎛ or less (i.e., pitch 40 ㎛ or less), more preferably 10/10. ㎛ or less, more preferably 5/5 ㎛ or less, even more preferably 1/1 ㎛ or less, particularly preferably 0.5/0.5 ㎛ 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 depends on the design of the circuit board, but is preferably 3 ㎛ to 35 ㎛, more preferably 5 ㎛ to 30 ㎛, more preferably 10 ㎛ to 20 ㎛, especially preferably 15 ㎛ to 15 ㎛. It is 20㎛. In addition, when the insulating layer is polished or ground after formation of the insulating layer 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 a thickness of It is desirable that it is different. Among each conductor layer, the thickness of the thickest conductor layer (conductive filler) 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. Additionally, the conductor layers connected between layers may be convex.

The conductor layer is, for example, a process of laminating a dry film (photosensitive resist film) on a substrate, exposing and developing the dry film under predetermined conditions using a photomask to form a pattern to obtain a patterned dry film. It can be formed by a method including a step of forming a conductor layer by a plating method such as electrolytic plating using the developed patterned dry film as a plating mask, and a step of peeling off the patterned 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 novolak resin or acrylic resin can be used. The conditions for laminating the substrate and the dry film may be the same as the conditions for laminating the substrate and the resin sheet, which will be described later. Peeling of the dry film can be performed, for example, using an alkaline peeling liquid such as 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 a conductor layer is formed on the surface of the substrate, the formation of the resin composition layer is preferably performed so that the conductor layer is embedded in the resin composition layer.

The resin composition layer is formed, for example, by laminating a resin sheet and a base material. This lamination can be performed, for example, by bonding the resin composition layer to the substrate by heat-pressing the resin sheet to the substrate from the support side. Examples of the member that heat-presses the resin sheet to the substrate (hereinafter sometimes referred to as “heat-press member”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls, etc.). there is. In addition, it is preferable not to press the heat-compression member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the base material.

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

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

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

After forming a resin composition layer on a substrate, the resin composition layer is heat-cured to form an insulating layer. The heat curing conditions of the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). range), 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).

Before thermally curing the resin composition layer, a preliminary heat treatment of heating the resin composition layer to a temperature lower than the curing temperature may be performed. For example, prior to heat curing the resin composition layer, the resin composition layer is usually cured at a temperature of 50°C or higher and less than 120°C (preferably 60°C or higher and 110°C or lower, more preferably 70°C or higher and 100°C or lower). You may preheat it, usually for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In the above manner, a circuit board with an insulating layer can be manufactured. In addition, the circuit board manufacturing method may further include an arbitrary process.

For example, when a circuit board is manufactured using a resin sheet, the method for manufacturing the circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled before heat curing of the resin composition layer, or may be peeled after heat curing of the resin composition layer.

The method of manufacturing a circuit board may include, for example, a step of forming an insulating layer and then polishing the surface of the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a flat grinding machine.

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

When performing an interlayer connection using a via hole, for example, a via hole is formed in an insulating layer formed on a base material with a wiring layer, and then a conductor layer is formed on the opposite side of the base material of the insulating layer to perform interlayer connection. . Examples of via hole formation methods include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferable. This laser irradiation can be performed using an appropriate laser processing machine using any light source such as a carbon dioxide gas laser, YAG laser, or 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 surface of the substrate.

Laser irradiation can be performed by an appropriate process according to the selected laser processing machine. The shape of the via hole is not particularly limited, but is generally circular or approximately circular. The shape of the via hole refers to the shape of the outline of the opening when viewed from the direction in which the via hole extends.

After forming the via hole, it is desirable to perform a process to remove smear within the via hole. This process is sometimes called a desmear process. For example, when forming a conductor layer over an insulating layer by a plating process, a wet desmear treatment may be performed on the via hole. Additionally, when forming the conductor layer on the insulating layer by a sputtering process, a dry desmear process such as a plasma treatment process may be performed. Additionally, a roughening treatment may be performed on the insulating layer by a desmear process.

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

After forming the via hole, a conductor layer is formed on the insulating layer. By forming a 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 connected, thereby establishing an interlayer connection. Methods for forming the conductor layer include, for example, a plating method, a sputtering method, and a vapor deposition method, and among these, 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. Additionally, when the support in the resin sheet is metal foil, a conductor layer having a desired wiring pattern can be formed by the subtractive method. The material of the conductor layer to be formed may be a single metal or an alloy. Additionally, this conductor layer may have a single-layer structure or a multi-layer structure containing two or more layers of different types of materials.

Here, an example of an embodiment of forming a conductor layer on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer, corresponding to the desired wiring pattern. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating. At that time, along with the formation of the electrolytic plating layer, the via hole may be filled by electrolytic plating to form a filled via. After forming the electrolytic plating layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or other processing to form a conductor layer having the desired wiring pattern. Additionally, when forming the conductor layer, the dry film used to form the mask pattern is the same as the dry film described above.

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

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

When performing interlayer connection 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 exposed on the side opposite to the substrate of the insulating layer. As the polishing and grinding method for the insulating layer, any method that can expose the conductor layer on the surface of the substrate can be used. Among them, a method in which a polished or ground surface parallel to the layer plane of the insulating layer is obtained by polishing or cutting is preferable. For example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as buffing, a surface grinding method using a grindstone rotation, etc. In addition, when performing interlayer connection by polishing or grinding the insulating layer, the smear removal process, the process of performing roughening treatment, and forming a conductor layer on the insulating layer are the same as when performing interlayer connection using via holes. You may perform the following process. Additionally, it is not necessary to expose the entire conductor layer on the surface of the substrate, and a portion of it may be exposed.

The circuit board manufacturing method may include, for example, step (4) of removing the substrate. By removing the base material, a circuit board having an insulating layer and a conductor layer embedded in the insulating layer can be obtained. This step (4) can be performed, for example, when a substrate having a peelable first metal layer and a second metal layer is used. Suitable examples will be described below. A conductor layer is formed on the surface of the second metal layer of a substrate having a first metal layer and a second metal layer. Additionally, 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 heat-cured to obtain an insulating layer. Thereafter, after performing interlayer connection as necessary, portions of the base material other than the second metal layer are peeled off. Then, the second metal layer is removed by etching with an etching solution such as an aqueous copper chloride solution. Thereby, removal of the substrate takes place. At this time, if necessary, the base material may be removed while the conductor layer is protected with a protective film.

In another embodiment, a circuit board can be manufactured using prepreg. The prepreg is a sheet-like fiber base material impregnated with a resin composition by, for example, a hot melt method or a solvent method. Examples of sheet-like fiber substrates include glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric. In addition, from the viewpoint of thinning, the thickness of the sheet-like fiber base 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 further preferably Typically, it is 1㎛ or more, 1.5㎛ or more, or 2㎛ or more. The thickness of this prepreg may be in the same range as the resin composition layer in the resin sheet described above. The manufacturing method of a circuit board using such a prepreg is basically the same as when using a resin sheet.

[13. Semiconductor chip package]

A semiconductor chip package according to the first embodiment of the present invention includes the above-described circuit board 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.

The bonding conditions between the circuit board and the semiconductor chip can be any conditions that allow conductor connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the circuit board. For example, conditions used in flip chip mounting of semiconductor chips can be adopted. Additionally, for example, a semiconductor chip and a circuit board may be bonded via an insulating adhesive.

An example of a bonding method is a method of pressing a semiconductor chip to a circuit board. As for the pressing conditions, the pressing 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 pressing time is usually 1 second to 60 seconds. range (preferably from 5 to 30 seconds).

Additionally, another example of a bonding method is a method of bonding a semiconductor chip to a circuit board by reflowing it. Reflow conditions may be in the range of 120°C to 300°C.

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

A semiconductor chip package according to a 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 semiconductor chip packages, the cured product of the resin composition usually functions as a sealing layer. Examples of the semiconductor chip package according to the second embodiment include a fan-out type WLP.

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. The semiconductor chip package 100 as a fan-out type WLP includes, for example, a semiconductor chip 110, as shown in FIG. 1; A sealing layer 120 formed to cover the periphery of the semiconductor chip 110; A redistribution forming layer 130 as an insulating layer provided on a side of the semiconductor chip 110 opposite to the sealing layer 120; A rewiring layer 140 as a conductor layer; Solder resist layer 150; and a bump 160.

The manufacturing method of such a semiconductor chip package is,

(A) A process of laminating a temporarily fixed film on a substrate,

(B) A process of temporarily fixing a semiconductor chip on a temporarily fixing film,

(C) Process of forming a sealing layer on a semiconductor chip,

(D) a process of peeling the substrate and temporarily fixed film from the semiconductor chip,

(E) A process of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled,

(F) a process of forming a redistribution layer as a conductor layer on the redistribution formation layer, and

(G) Process of forming a solder resist layer on the redistribution layer,

Includes. In addition, the method for manufacturing the above semiconductor chip package is,

(H) Process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces.

It may be included. Hereinafter, this manufacturing method will be described in detail.

(Process (A))

Process (A) is a process of laminating a temporarily fixed film on a substrate. The laminating conditions of the base material and the temporarily fixed film may be the same as the laminating conditions of the base material and the resin sheet in the circuit board manufacturing method.

As a base material, for example, a silicon wafer; glass wafer; glass substrate; Metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); A substrate such as an FR-4 substrate, which is heat-cured by impregnating glass fiber with an epoxy resin or the like; A substrate made of bismaleimide triazine resin such as BT resin; etc. can be mentioned.

The temporarily fixed film can be peeled from the semiconductor chip, and any material that can temporarily fix the semiconductor chip can be used. Commercially available products include "River Alpha" manufactured by Nitto Denko Co., Ltd.

(Process (B))

Process (B) is a process of temporarily fixing the semiconductor chip on the temporarily fixing film. Temporary fixation of a semiconductor chip can be performed, for example, using devices such as a flip chip bonder or die bonder. The layout and number of batches of semiconductor chips can be appropriately set depending on the shape and size of the temporarily fixed film, the production number of the intended semiconductor package, etc. For example, semiconductor chips may be aligned and temporarily fixed in a matrix of multiple rows and multiple columns.

(Process (C))

Step (C) is a step of forming a sealing layer on the semiconductor chip. The sealing layer is formed from a cured product of the above-mentioned resin composition. 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 heat curing this resin composition layer to form a sealing layer.

Taking advantage of the excellent compression moldability of the resin composition, the formation of the resin composition layer is preferably performed by a compression molding method. In the compression molding method, a semiconductor chip and a resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the resin composition within the mold to form a resin composition layer that covers the semiconductor chip.

Specific operations of the compression molding method can be performed, for example, as follows. As a mold for compression molding, prepare an upper mold and a lower mold. Additionally, the resin composition is applied to the semiconductor chip temporarily fixed on the temporarily fixed film as described above. The semiconductor chip coated with the resin composition is attached to the lower mold along with the base material and the temporarily fixed film. Thereafter, the upper and lower molds are clamped, heat and pressure are applied to the resin composition, and compression molding is performed.

In addition, the specific operation of the compression molding method may be performed as follows, for example. As a mold for compression molding, prepare an upper mold and a lower mold. The resin composition is placed on the lower mold. Additionally, a semiconductor chip is attached to the upper mold together with a base material and a temporarily fixed film. Thereafter, the upper and lower molds are clamped so that the resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

Molding conditions vary depending on the composition of the resin composition, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold 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, and particularly preferably 120°C or higher. , and is preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. In addition, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. . The cure time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, especially preferably 20 minutes or less. am. Usually, after forming the resin composition layer, the mold is separated. Separation of the mold may be performed before or after thermal curing of the resin composition layer.

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

After forming a resin composition layer on the semiconductor chip, this resin composition layer is heat-cured to obtain a sealing layer that covers the semiconductor chip. As a result, the semiconductor chip is sealed with the cured resin composition. The heat curing conditions of the resin composition layer may be the same as the heat curing conditions of the resin composition layer in the circuit board manufacturing method. Additionally, before heat curing the resin composition layer, a preliminary heat treatment of heating the resin composition layer to a temperature lower than the curing temperature may be performed. The processing conditions for this preliminary heat treatment may be the same as those for the preliminary heat treatment in the circuit board manufacturing method.

(Process (D))

Process (D) is a process of peeling the base material and the temporarily fixed film from the semiconductor chip. As for the peeling method, it is preferable to adopt an appropriate method depending on the material of the temporarily fixed film. Examples of the peeling method include a method of peeling the temporarily fixed film by heating, foaming, or expanding it. Moreover, as a peeling method, for example, a method of peeling by irradiating ultraviolet rays to a temporarily fixed film through a base material, reducing the adhesive force of a temporarily fixed film, is mentioned.

In the method of peeling a temporarily fixed film by heating, foaming, or expanding it, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of peeling the temporarily fixed film by irradiating ultraviolet rays to lower the adhesive force, the irradiation amount of ultraviolet rays is usually 10 mJ/cm2 to 1000 mJ/cm2.

(Process (E))

Step (E) is a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film have been peeled.

The material for the redistribution formation layer can be any material that has insulating properties. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Additionally, as this thermosetting resin, the resin composition of the present invention may be used.

After forming the redistribution forming layer, a via hole may be formed in the redistribution forming layer to interlayer connect the semiconductor chip and the redistribution layer.

In the method of forming a via hole when the material of the redistribution layer is a photosensitive resin, an active energy ray is usually irradiated to the surface of the redistribution layer through a mask pattern, and the redistribution layer in the irradiated portion is photocured. Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately set depending on the photosensitive resin. Examples of the exposure method include a contact exposure method that exposes the mask pattern while bringing it into close contact with the redistribution layer, and a non-contact exposure method that exposes the mask pattern using parallel light without bringing it into close contact with the redistribution layer.

After photocuring the redistribution forming layer, the redistribution forming layer is developed, the unexposed portion is removed, and a via hole is formed. Development may be performed by either wet development or dry development. Examples of the development method include the dip method, paddle method, spray method, brushing method, scraping method, etc., and the paddle method is suitable from the viewpoint of resolution.

Examples of via hole formation methods when the material of the redistribution formation layer is a thermosetting resin include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is preferable. Laser irradiation can be performed using an appropriate laser processing machine using a light source such as a carbon dioxide gas laser, UV-YAG laser, or excimer laser.

The shape of the via hole is not particularly limited, but is generally circular (approximately 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 less. That's it. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the redistribution formation layer.

(Process (F))

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

(Process (G))

Process (G) is a process of forming a solder resist layer on the redistribution layer. The material of the solder resist layer can be any material that has insulating properties. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of ease of manufacturing semiconductor chip packages. Additionally, the resin composition of the present invention may be used as a thermosetting resin.

Additionally, in step (G), bumping processing to form bumps may be performed, if necessary. Bumping processing can be performed using methods such as solder balls and solder plating. In addition, formation of via holes in bumping processing can be performed in the same manner as step (E).

(Process (H))

The method for manufacturing a semiconductor chip package may include a step (H) in addition to steps (A) to (G). Process (H) is a process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual semiconductor chip packages. The method of dicing a 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 semiconductor chip package 100 as shown in FIG. 1, a redistribution formation layer 130 or a solder resist layer 150. It is a semiconductor chip package formed from a cured product of the resin composition of the invention.

[14. semiconductor device]

Examples of semiconductor devices on which the above-described semiconductor chip package is mounted include electrical appliances (e.g., computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, etc.) and electronic devices. Examples include various semiconductor devices provided for things (e.g., two-wheeled vehicles, automobiles, trams, ships, aircraft, etc.).

[Example]

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In addition, the operations described below were performed in an environment at room temperature and pressure, unless otherwise specified.

[Method for measuring viscosity of epoxy resin]

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

[Example 1]

Liquid polybutadiene epoxy resin (“JP400” manufactured by Nihon Soda Co., Ltd., epoxy equivalent weight 230, number average molecular weight Mn=3500, viscosity 5.5 Pa·s at 45°C, glass transition temperature - 62°C) 2 parts, N-phenyl-3 - 90 parts of spherical silica (average particle diameter 3.5 ㎛, specific surface area 3.7 m2/g) surface-treated with aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), acid anhydride curing agent (manufactured by Shin-Nippon Rika Corporation) "HNA-100", acid anhydride equivalent 179) 10 parts, glycidylamine type epoxy resin ("EP-3980S" manufactured by ADEKA, epoxy equivalent 115) 3 parts, glycidylamine type epoxy resin (manufactured by Mitsubishi Chemical Corporation) “630”, epoxy equivalent 95) 7 parts, bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC, epoxy equivalent 173) 3 parts, imidazole-based curing accelerator (“2E4MZ” manufactured by Shikoku Kasei) 0.1 part, mixer was mixed to obtain a resin composition.

[Example 2]

Instead of 10 parts of the acid anhydride curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd.), 5 parts of a cresol novolak-type curing agent (“KA-1160” manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent weight 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 the acid anhydride curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd.), 5 parts of a liquid novolak-type phenol curing agent (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent weight 141) was used.

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.

Additionally, instead of 3 parts of bisphenol A type epoxy resin (“EXA-850CRP” manufactured by DIC), 2 parts of aliphatic epoxy resin (“YED-216D” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 120) was used.

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 the acid anhydride curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd.), 5 parts of a liquid novolak-type phenol curing agent (“MEH-8000H” manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent weight 141) was used.

Additionally, instead of 7 parts of glycidylamine type epoxy resin (“630” manufactured by Mitsubishi Chemical Company), 7 parts of glycidylamine type epoxy resin (“ELM-100H” manufactured by Tsumitomo Chemical Company, epoxy equivalent 106) was used. .

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 (“JP400” manufactured by Nihon Soda Co., Ltd.), polybutadiene epoxy resin (“JP-200” manufactured by Nippon Soda Co., Ltd., epoxy equivalent weight 210 to 240, number average molecular weight Mn=2200, at 45°C Viscosity of 100 Pa·s) 2 parts were used.

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 (“JP400” manufactured by Nippon Soda Co., Ltd.), polybutadiene epoxy resin (“PB-3600” manufactured by Daicel Co., Ltd., epoxy equivalent weight 193, number average molecular weight Mn=5900, viscosity at 45°C 45Pa ·s) 2 parts were used.

Additionally, instead of 10 parts of the acid anhydride curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd.), 5 parts of a cresol novolak-type curing agent (“KA-1160” manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent weight: 117) was used.

Except for the above, the same operation as in Example 1 was performed to obtain a resin composition.

[Comparative Example 3]

Liquid polybutadiene epoxy resin (“JP400” manufactured by Nihon Soda Corporation) was not used.

Additionally, instead of 10 parts of the acid anhydride curing agent (“HNA-100” manufactured by Nippon Rika Co., Ltd., acid anhydride equivalent weight 179), 5 parts of a cresol novolak-type curing agent (“KA-1160” manufactured by DIC Co., Ltd., phenolic hydroxyl group equivalent weight 117) was used. used.

Additionally, 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 coefficient of linear thermal expansion (CTE) of cured resin composition]

(Production of hardened product for evaluation)

A polyethylene terephthalate film (“501010” manufactured by Lintec, thickness 38 μm, 240 mm square) on which one side had undergone release treatment was prepared. On the untreated side of the polyethylene terephthalate film that has not been subjected to release treatment, a glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Denko, thickness 0.7 mm, 255 mm square) is placed on top of each other, and the four sides are adhered with polyimide. It was fixed with tape (width 10 mm). As a result, a fixed PET film containing a polyethylene terephthalate film and a glass cloth-based epoxy resin double-sided copper-clad laminate was obtained.

Methyl ethyl ketone was added to the resin composition prepared in Examples and Comparative Examples to dilute it, and the viscosity of the resin composition was adjusted to 4000 mPa·s. Additionally, as a support, a polyethylene terephthalate film (“Lumira R80” manufactured by Torre, thickness 38 μm, softening point 130°C) was prepared, the surface of which had been subjected to a release treatment with an alkyd resin-based release agent (“AL-5” manufactured by Lintec). did. 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 (thickness of the resin composition layer was 100 μm) was cut into a 200 mm square. The cut resin sheet is used in a batch-type vacuum pressurized laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials), and the resin composition layer is applied to the polyethylene terephthalate film side of the fixed PET film (i.e., mold release treatment). was laminated so that it was in contact with the center of the surface where was applied, to obtain a multi-layer sample. The above laminate was performed by reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less, and then pressing it at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

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

After the above thermal curing, the polyimide adhesive tape was peeled off, the glass cloth base epoxy resin double-sided copper clad laminate was peeled off, and the polyethylene terephthalate film was further peeled off to obtain a cured product of the sheet-like resin composition. The obtained cured product may be referred to as “cured product for evaluation.”

(CTE measurement)

The above cured product for evaluation was cut into pieces with a width of 5 mm and a length of 15 mm to obtain a test piece. Thermomechanical analysis was performed on this test piece by the tensile weighting method using a thermomechanical analysis device (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). In detail, after the test piece was mounted on the thermomechanical analysis device, measurements were performed twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. And in the second measurement, the linear thermal expansion coefficient (ppm/°C) in the planar direction in the range from 25°C to 150°C was calculated.

[Measurement of bending amount]

On a 12-inch silicon wafer, the resin compositions prepared in Examples and Comparative Examples were compression molded using a compression mold device (mold temperature: 130°C, pressure: 6MPa, cure time: 10 minutes) to form a resin with a thickness of 300 μm. A composition layer was formed. After that, the resin composition layer was heat-cured by heating at 180°C for 90 minutes. As a result, a sample substrate including a silicon wafer and a cured layer of the resin composition was obtained.

Using a shadow moiré measurement device (“ThermoireAXP” manufactured by Akorometrix), the amount of warpage when the sample substrate was heated and cooled in that order at 35°C, 260°C, and 35°C was measured. Measurements were performed in accordance with JEITA EDX-7311-24 of the Electronic Information Technology Industry Association standard. Specifically, the virtual plane calculated by the least squares method of all data on the substrate surface in the measurement area was used as a reference plane, and the difference between the minimum and maximum values in the vertical direction from the reference plane was obtained as the amount of warpage. A warp amount of less than 2 mm was judged as “good” and a warp amount of 2 mm or more was judged as “bad.”

[Evaluation of adhesion]

A thermal release sheet (Thermal release tape; "Riva Alpha" manufactured by Nitto Denko Co., Ltd.), which has adhesiveness at room temperature and can be easily peeled off when heated, was attached to a 12-inch silicon wafer. On this thermal release sheet, 100 1 cm square silicon chips (thickness 400 μm) were placed at equal intervals. Next, the resin compositions prepared in Examples and Comparative Examples were compression molded on the thermal release sheet on which the silicon chip was placed using a compression mold device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes), A resin composition layer with embedded silicon chips and a layer thickness of 500 μm was formed. The thermal release sheet was brought into a peelable state by heating at 180°C, and the thermal release sheet and silicon wafer were removed. After that, the resin composition layer was heated at 180°C for 90 minutes to heat-cure the resin composition layer. As a result, a resin wafer containing a cured layer of the resin composition and a silicon chip embedded in the cured layer was obtained.

Afterwards, a thermal cycle test was performed on the resin wafer. This thermal cycle test is a test in which cooling to -55°C and heating to 125°C constitute one cycle, and the cooling and heating are repeated 1000 cycles. After the thermal cycle test, the resin wafer was observed, and cases where delamination occurred at the interface between the silicon chip and the cured material layer were judged as "bad", and cases where delamination did not occur were judged as "good." Additionally, when cracks occurred on the surface of the resin composition layer after compression molding of the resin composition, it was determined to be a “crack.”

[Evaluation of compression moldability]

On a 12-inch silicon wafer, the resin compositions prepared in Examples and Comparative Examples were compression molded using a compression mold device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) to form a resin with a thickness of 300 μm. A composition layer was formed. Afterwards, the resin composition layer was observed, and the case where the resin composition was able to be filled up to the end of the wafer was rated as “good”; the case where underfilling occurred was “bad”; and the case where cracks occurred on the surface of the resin composition layer after compression molding was rated as “good.” It was judged to be a “crack.”

[Method for measuring dielectric loss tangent]

The resin compositions prepared in Examples and Comparative Examples were compression molded on a SUS plate whose surface had been subjected to mold release treatment using a compression mold device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). A resin composition layer with a thickness of 300 μm was formed. The SUS plate was peeled off, and the resin composition layer was heat-cured by heating at 180°C for 90 minutes to obtain a cured layer of the resin composition. This cured layer was cut to 80 mm in length and 2 mm in width to obtain an evaluation sample for dielectric loss tangent measurement. For this evaluation sample, the dielectric loss tangent was measured by the cavity resonance perturbation method using an analysis device (“HP8362B” manufactured by Agilent Technologies) at a measurement temperature of 23°C and a measurement frequency of 5.8 GHz.

[result]

The results of the above-mentioned examples and comparative examples are shown in the table below.

[Table 1]

[Table 1. Results of examples and comparative examples]

[examine]

As can be seen from Table 1, the resin composition according to the example has excellent compression moldability. In addition, the cured product of the resin composition according to the example has a low coefficient of linear thermal expansion, can suppress warping, and is excellent in high adhesion even after repeated heating and cooling. Therefore, by the present invention, it is possible to obtain a cured product that has a low coefficient of linear thermal expansion, can suppress warping, and achieves high adhesion even after repeated heating and cooling, and can also realize a resin composition layer with excellent compression moldability. This has been confirmed.

In addition, by comparing Examples with Comparative Example 3, which does not use an epoxy resin having an alkene skeleton in the molecule, the resin composition of the present invention using an epoxy resin having an alkene skeleton in the molecule generally has a low dielectric loss tangent. It was confirmed that the cargo was obtained.

In addition, in Examples 1 to 5, it was confirmed that even when components (D) to (E) were not contained, the same results as the above examples were obtained, although there was a difference in degree.

100 semiconductor chip packages
110 semiconductor chip
120 sealing layer
130 Rewiring cambium
140 rewiring layer
150 solder resist layer
160 bump

Claims (16)

(A) An epoxy resin having a viscosity of 20 Pa·s or less at 45°C, a number average molecular weight of 2500 or more, and an alkene skeleton in the molecule,
(B) inorganic filler;
(C) a curing agent, and
Contains (D) epoxy resin other than component (A),
A resin composition in which the amount of component (D) is 500 parts by mass or more and 1,000 parts by mass or less with respect to 100 parts by mass of component (A). The resin composition according to claim 1, wherein component (A) has a polybutadiene structure in the molecule. The resin composition according to claim 1, wherein component (A) has a viscosity of 15 Pa·s or less at 45°C. The resin composition according to claim 1, wherein the average particle diameter of component (B) is 0.1 μm to 10 μm. The resin composition according to claim 1, wherein component (C) is an acid anhydride-based curing agent or a phenol-based curing agent. The resin composition according to claim 1, further comprising (E) a curing accelerator. The resin composition according to claim 1, which is a solvent-free resin composition that does not contain a solvent. The resin composition according to claim 1, wherein the cured product obtained by heating the resin composition at 190°C for 90 minutes has a linear thermal expansion coefficient in the range from 25°C to 150°C of 10 ppm/°C or less. The resin composition according to claim 1, wherein the cured product obtained by heating the resin composition at 180° C. for 90 minutes has a dielectric loss tangent of 0.007 or less. The resin composition according to claim 1, which is a resin composition for semiconductor encapsulation or insulating layer. The resin composition according to claim 1, which is a resin composition for fan-out type WLP or fan-out type PLP. The resin composition according to claim 1, which is a liquid resin composition. A resin sheet having a support and a resin composition layer containing the resin composition according to any one of claims 1 to 12 provided on the support. A circuit board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 12. A semiconductor chip package comprising the circuit board according to claim 14 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip and a cured product of the resin composition according to any one of claims 1 to 12 that seals the semiconductor chip.

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