TW202342638A - Resin composition and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition that can improve the heat dissipation properties of the obtained cured product and improve the flexibility of the obtained cured product. The resin composition of the present invention contains a thermosetting resin and an insulating filler. The maximum particle diameter of the insulating filler is 45 μm or less. When a cured product of the resin composition is obtained by heating at 150° C. for 2 hours, the cured product The thermal conductivity is above 1.0 W/m･K, and the storage modulus of the above-mentioned hardened material at 25°C is below 2000 MPa.

Description

Resin composition and semiconductor device

The present invention relates to a resin composition containing a thermosetting resin and an insulating filler. Furthermore, the present invention relates to a semiconductor device using a cured product of the above-mentioned resin composition.

In recent years, as electronic equipment has become more sophisticated, the amount of heat generated in semiconductor devices has been increasing. When electronic equipment is continuously used, heat may be transferred to the semiconductor element (wafer), causing warping of the substrate or the semiconductor element (wafer). Therefore, the necessity of dissipating heat from electronic components increases. To dissipate heat, die attach materials containing insulating fillers are used.

In addition, when manufacturing semiconductor devices used in electronic equipment, the semiconductor device may be heated to a high temperature and then slowly cooled to room temperature. At this time, internal stress is applied to the substrate or semiconductor element (wafer) due to the difference in linear expansion between the substrates. Due to this internal stress, warpage may occur in the substrate or semiconductor element (wafer).

Furthermore, as electronic devices become larger in capacity and have higher pixels, semiconductor elements (wafers) are gradually enlarged, and the above-mentioned problem of substrate or semiconductor element (wafer) warping is more likely to occur.

Patent Document 1 below discloses a semiconductor protection material that is coated on the surface of a semiconductor element to protect the semiconductor element. The semiconductor protection material includes a flexible epoxy compound, an epoxy compound different from the above-mentioned flexible epoxy compound, a hardener that is liquid at 23°C, a hardening accelerator, and a thermal conductivity of 10 W/m ･K or above and spherical inorganic filler.

In the following Patent Document 2, a curable resin composition is disclosed, which contains: (A) epoxy resin; (B) inorganic filler, in the particle size distribution, the most frequent particle diameter is 0.1 μm to 10 μm; and (C) dispersant, which has a specific phosphate group. [Prior technical literature] [Patent Document]

[Patent Document 1] WO2016/010067A1 [Patent Document 2] Japanese Patent Application Publication No. 2016-098312

[Problem to be solved by the invention]

The semiconductor protection material described in Patent Document 1 is different from the die adhesive material. In addition, in the case of a grain adhesive material containing an inorganic filler with a large particle size, it is difficult to apply the filler thinly on the surface of the substrate. As a result, there is a problem that heat dissipation cannot be sufficiently improved and warpage of the substrate or semiconductor element (wafer) cannot be suppressed.

Furthermore, in Patent Document 2, there is a problem that since the cured product of the curable resin composition is very hard, internal stress during production cannot be relaxed and warpage of the substrate or semiconductor element (wafer) cannot be suppressed.

An object of the present invention is to provide a resin composition that can improve the heat dissipation properties of the obtained cured product and improve the flexibility of the obtained cured product. Furthermore, another object of the present invention is to provide a semiconductor device using a cured product of the above-mentioned resin composition. [Technical means to solve problems]

In a broad aspect of the present invention, a resin composition can be provided, which contains a thermosetting resin and an insulating filler. The maximum particle size of the insulating filler is 45 μm or less. The above-mentioned composition is obtained by heating at 150° C. for 2 hours. In the case of a cured product of the resin composition, the thermal conductivity of the cured product is 1.0 W/m･K or more, and the storage modulus of the cured product at 25°C is 2000 MPa or less.

In a specific aspect of the resin composition of the present invention, the thermal conductivity of the insulating filler is 10 W/m･K or more.

In a specific aspect of the resin composition of the present invention, the viscosity at 25°C and 10 rpm is 150 Pa･s or less.

In a specific aspect of the resin composition of the present invention, the ratio of the viscosity at 25°C and 1 rpm to the viscosity at 25°C and 10 rpm is 2.0 or more.

In a specific aspect of the resin composition of the present invention, the thermosetting resin includes an epoxy resin.

In a specific aspect of the resin composition of the present invention, the epoxy resin includes a flexible epoxy resin.

In a specific aspect of the resin composition of the present invention, the content of the flexible epoxy resin is 30% by weight or more and 90% by weight or less in 100% by weight of the above-mentioned epoxy resin.

In a specific aspect of the resin composition of the present invention, the flexible epoxy resin includes polyalkylene glycol diglycidyl ether.

In a specific aspect of the resin composition of the present invention, the epoxy equivalent of the flexible epoxy resin is 300 g/eq or more and 1000 g/eq or less.

In a specific aspect of the resin composition of the present invention, the resin composition further includes a thermosetting agent, the thermosetting agent includes a polymer of a butadiene compound, and the polymer of the butadiene compound has two or more properties. The content of the polymer of the butadiene compound in the thermal hardener is 25 parts by weight or more relative to 100 parts by weight of the epoxy resin as a functional group that reacts with the epoxy group of the epoxy resin.

In a specific aspect of the resin composition of the present invention, the insulating filler is made of alumina, synthetic magnesite, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide.

In a specific aspect of the resin composition of the present invention, the maximum particle size of the insulating filler is 25 μm or less.

In a specific aspect of the resin composition of the present invention, in the volume-based particle size distribution of the above-mentioned insulating filler, there is a region with a particle diameter of 0.1 μm or more and less than 1.0 μm and a particle size of 1.0 μm or more and 10 μm or less. There are peaks in the region.

In a specific aspect of the resin composition of the present invention, the above-mentioned resin composition further includes a dispersant, the amine value of the above-mentioned dispersant is 40 KOHmg/g or more and 95 KOHmg/g or less, and the acid value of the above-mentioned dispersant is 45 KOHmg /g and above 95 KOHmg/g and below.

In a specific aspect of the resin composition of the present invention, the resin composition is a die attach paste.

According to a broad aspect of the present invention, a semiconductor device can be provided, which includes a substrate, a die adhesive material arranged on the surface of the substrate, and a semiconductor element arranged on the surface of the die adhesive material. The die adhesive material The material is a hardened product of the above-mentioned resin composition.

According to a broad aspect of the present invention, a semiconductor device can be provided, which includes a substrate, a die adhesive material arranged on the surface of the substrate, and a semiconductor element arranged on the surface of the die adhesive material. The die adhesive material The material is a cured product of a resin composition containing a thermosetting resin and an insulating filler. The maximum particle size of the insulating filler is 45 μm or less. The thermal conductivity of the cured product is 1.0 W/m･K or more. The storage modulus at 25℃ is below 2000 MPa. [Effects of the invention]

The resin composition of the present invention contains a thermosetting resin and an insulating filler. The maximum particle diameter of the insulating filler is 45 μm or less. When a cured product of the resin composition is obtained by heating at 150° C. for 2 hours, the cured product The thermal conductivity is above 1.0 W/m･K, and the storage modulus of the above-mentioned hardened material at 25°C is below 2000 MPa. In the resin composition of the present invention, since it has the above-described structure, the heat dissipation properties of the obtained cured product can be improved, and the flexibility of the obtained cured product can be improved.

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention contains a thermosetting resin and an insulating filler. In the resin composition of the present invention, the maximum particle size of the insulating filler is 45 μm or less. In the resin composition of the present invention, when the cured product of the above-mentioned resin composition is obtained by heating at 150°C for 2 hours, the thermal conductivity of the above-mentioned cured product is 1.0 W/m･K or more, and the thermal conductivity of the above-mentioned cured product at 25°C The storage modulus below is below 2000 MPa.

In the conventional resin composition, since the particle size of the insulating filler is large, it is difficult to coat the insulating filler thinly on the substrate when used as a die adhesive paste. As a result, there is a problem that the cured product of the resin composition cannot sufficiently improve heat dissipation and cannot suppress warpage of the substrate or semiconductor element (wafer). Furthermore, conventional resin compositions have had the following problems: since the cured product of the resin composition is very hard, internal stress during production cannot be relaxed and warpage of the substrate or semiconductor element (wafer) cannot be suppressed.

When the cured product of the resin composition has insufficient heat dissipation or flexibility like the conventional resin composition, warpage of the substrate or semiconductor element (wafer) is likely to occur. In addition, this problem becomes more significant due to the enlargement of semiconductor devices (wafers).

For example, when die adhesive is used in a sensor inside a camera module, the displayed image may be deformed due to warping of the substrate or semiconductor element (chip).

Since the resin composition of the present invention has the above-mentioned structure, it can be applied thinly to a substrate or the like, and the heat dissipation properties of the cured product can be sufficiently improved. Furthermore, since the resin composition of the present invention has the above-mentioned structure, internal stress during production can be relaxed. That is, in the cured product of the resin composition of the present invention, it is possible to achieve both high heat dissipation and high flexibility, which was previously difficult to achieve. As a result, warpage of the substrate or semiconductor element (wafer) can be suppressed.

Furthermore, since the resin composition of the present invention has the above-mentioned structure, it can be used even when it is used for semiconductor elements (wafers) having a large area or for semiconductor devices that are expected to become high-temperature due to continuous use for a long time. In this case, the warpage of the substrate or semiconductor element (wafer) can also be suppressed.

Furthermore, in order to improve the productivity of semiconductor devices and the like, a resin composition that can be cured at low temperature and in a short time is required.

Since the resin composition of the present invention has the above-mentioned structure, it can be cured at low temperature and in a short time. As a result, the productivity of semiconductor devices using the above resin composition can be improved.

The viscosity of the above-mentioned resin composition at 25°C and 10 rpm is preferably above 10 Pa･s, more preferably above 20 Pa･s, and preferably below 150 Pa･s, and more preferably below 100 Pa･s. , and more preferably 80 Pa･s or less. If the viscosity of the above-mentioned resin composition at 25° C. and 10 rpm is above the above-mentioned lower limit and below the above-mentioned upper limit, the heat dissipation property of the obtained cured product can be improved, and the flexibility of the obtained cured product can be improved.

The ratio (thixotropic index) of the viscosity at 25°C and 1 rpm to the viscosity at 25°C and 10 rpm of the resin composition is preferably 2.0 or more, more preferably 2.5 or more, and further preferably 3.0 or more . When the thixotropic index is equal to or higher than the lower limit, the coating properties of the resin composition can be improved. The upper limit of the above-mentioned thixotropy index is not particularly limited. The thixotropic index may be 7.0 or less, or 5.0 or less.

The viscosity of the above-mentioned resin composition at 25°C and 1 rpm, and the viscosity at 25°C and 10 rpm can be measured using a B-type viscometer. Examples of the above-mentioned B-type viscometer include "TVB-10 type" manufactured by Toki Industrial Co., Ltd.

When measuring the viscosity using the above-mentioned B-type viscometer, when the object to be measured is of low viscosity (for example, the viscosity at 25°C and 100 rpm is less than 10 Pa･s), the spindle for low viscosity (TH6-TH1) can be used Make a determination. In the measurement of viscosity using the above-mentioned B-type viscometer, when the object of measurement is medium to high viscosity (for example, the viscosity at 25°C and 100 rpm is more than 10 Pa･s), the spindle for medium and high viscosity can be used (TH1) for measurement.

From the viewpoint of further improving the coatability of the resin composition, the resin composition is preferably liquid at 25°C and not solid at 25°C. From the viewpoint of further improving the heat dissipation properties of the obtained cured product, the resin composition is preferably a resin paste. Furthermore, liquid also includes viscous pastes.

From the viewpoint of exhibiting the effects of the present invention more effectively, the resin composition is preferably a die attach paste. The above-mentioned resin composition is suitable for use as a die attach paste.

(hardened product of resin composition) In the resin composition of the present invention, when the cured product of the above-mentioned resin composition is obtained by heating at 150°C for 2 hours, the thermal conductivity of the above-mentioned cured product is 1.0 W/m･K or more, and the thermal conductivity of the above-mentioned cured product at 25°C The storage modulus below is below 2000 MPa.

The above-mentioned cured product is a cured product of the above-mentioned resin composition, and is obtained by curing the above-mentioned resin composition. Furthermore, the thickness of the hardened material is not particularly limited. The thickness of the above-mentioned hardened material may be 5 μm or more, 10 μm or more, or 20 μm or more. In addition, the thickness of the hardened material may be 500 μm or less, 100 μm or less, or 25 μm or less.

The thermal conductivity of the hardened material is preferably 1.2 W/m･K or more, more preferably 1.5 W/m･K or more, further preferably 2.0 W/m･K or more, and more preferably 10.0 W/m･ K or less, more preferably 6.0 W/m･K or less, still more preferably 5.0 W/m･K or less. If the thermal conductivity of the hardened material is equal to or higher than the lower limit, warpage of the semiconductor element (wafer) can be suppressed.

The thermal conductivity of the above-mentioned hardened material can be measured by the following method, for example. Use an applicator to coat the resin composition on the surface of the substrate with a thickness of 500 μm. Then, it was heated at 150° C. for 2 hours using a dryer to harden, thereby obtaining a test sample (hardened material) of 100 mm × 100 mm × 500 μm in thickness. The thermal conductivity of the obtained test sample is measured using a thermal conductivity meter (for example, "Quick Thermal Conductivity Meter QTM-500" manufactured by Kyoto Electronics Industry Co., Ltd.).

The storage modulus of the hardened material at 25°C is preferably 1500 MPa or less, more preferably 1000 MPa or less, further preferably 500 MPa or less, particularly preferably 300 MPa or less, and most preferably 100 MPa or less. If the storage modulus of the cured product at 25°C is below the upper limit, the flexibility of the cured product can be further improved, and warpage of the semiconductor element (wafer) can be suppressed. There is no particular lower limit on the storage modulus of the above-mentioned hardened material at 25°C. The storage modulus of the above-mentioned hardened material at 25°C may be more than 100 MPa or more than 300 MPa.

The storage modulus of the above-mentioned hardened material at 25° C. can be measured, for example, by the following method. Use an applicator to coat the resin composition on the surface of the substrate with a thickness of 500 μm. Then, it was heated at 150°C for 2 hours using a dryer to harden, and a test sample (hardened material) of 20 mm×5 mm×500 μm in thickness was obtained. For the obtained test sample, a forced vibration type dynamic viscoelasticity measuring device (such as "DVA-200" manufactured by Japan IT Measurement Control Company) was used under tensile conditions, frequency 10 Hz, strain 0.1%, and temperature range 0°C. The measurement is carried out under the conditions of ~150℃ and a temperature rise rate of 2℃/min. The measured value at 25℃ is regarded as the storage modulus.

The storage modulus of the above-mentioned cured product at 25° C. can be increased, for example, by increasing the degree of cross-linking in the thermosetting resin described below, stretching the above-mentioned thermosetting resin, and the like. In addition, the storage modulus of the cured product at 25° C. can be reduced by increasing the number average molecular weight and lowering the glass transition temperature of the thermosetting resin.

From the viewpoint of hardening the resin composition at a lower temperature and in a shorter time, the reaction rate in the cured product obtained by heating and hardening the resin composition at 150° C. for 15 minutes is preferably 85% or more, and more preferably 85% or more. The best is 90% or more, the further best is 95% or more, and the extremely best is 99% or more. The above reaction rate may also be 100%.

The above reaction rate can be measured by the following method. Use an applicator to apply the resin composition to a thickness of 50 μm on the surface of the substrate. Then, it was heated at 150°C for 15 minutes using a dryer to harden, and a test sample (hardened material) of 100 mm×100 mm×50 μm in thickness was obtained. Then, the test sample was crushed with a mortar to obtain a crushed product. For the obtained crushed materials, a differential scanning calorimetry (DSC) device (such as "EXSTAR DSC7020" manufactured by SII Corporation) is used in a nitrogen atmosphere in the range of -50°C to 150°C and a temperature rise rate of 5°C/min. Under the conditions, measure the exothermic peak area B of the broken material. The exothermic peak area A of the resin composition before curing is measured in the same manner. The reaction rate was calculated as "reaction rate (%)=(1-(exothermic peak area B/exothermic peak area A))×100".

The cured product of the above resin composition is preferably used as a die bonding material. The cured product of the above resin composition is particularly suitable as a die attach material for semiconductor devices.

The components contained in the resin composition of the present invention will be described below.

(Thermosetting resin) Examples of the thermosetting resin include epoxy resin, polyphenylene ether resin, divinyl benzyl ether resin, polyarylate resin, diallyl phthalate resin, polyimide resin, and benzene resin. 𠯤Resin, benzozoazole resin, bismaleimide resin and acrylic resin, etc. Only one type of the above-mentioned thermosetting resin may be used, or two or more types may be used in combination.

From the viewpoint of further improving the heat dissipation and flexibility of the obtained cured product, the thermosetting resin preferably contains an epoxy resin, a silicone resin, or an acrylic resin, and more preferably contains an epoxy resin. Only one type of the above-mentioned epoxy resin may be used, or two or more types may be used in combination.

From the viewpoint of further improving the flexibility of the obtained cured product, the epoxy resin preferably contains a flexible epoxy resin. Only one type of the above-mentioned flexible epoxy resin may be used, or two or more types may be used in combination. The above-mentioned epoxy resin may also include epoxy resins other than flexible epoxy resin.

The indicators of flexibility in flexible epoxy resin are as follows. Epoxy resins are defined as flexible epoxy resins when the stoichiometric amount of diethylenetriamine (DETA) is hardened and the Shore D hardness tester is less than 30.

Examples of the flexible epoxy resin include polyalkylene glycol diglycidyl ether, polybutadiene diglycidyl ether, sulfide-modified epoxy resin, and polyalkylene oxide-modified bisphenol A. Type epoxy resin, aliphatic modified epoxy resin, ε-caprolactone modified epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, amine modified epoxy resin, and Dimer acid modified epoxy resin, etc. From the viewpoint of further improving the flexibility of the obtained cured product, the flexible epoxy resin preferably has two or more epoxy groups. From the viewpoint of further improving the flexibility of the obtained cured product, the flexible epoxy resin preferably contains polyalkylene glycol diglycidyl ether, and more preferably contains polyalkylene glycol diglycidyl ether which does not have a bisphenol skeleton. Alkyl glycol diglycidyl ether.

From the viewpoint of further improving the flexibility of the obtained cured product, the polyalkylene glycol diglycidyl ether preferably has 8 or more alkylene glycol group repeating structural units. From the viewpoint of further improving the flexibility of the obtained cured product, the polyalkylene glycol diglycidyl ether more preferably has 10 or more alkylene glycol group repeating structural units. The upper limit of the repeating number of the above-mentioned alkylene glycol group is not particularly limited. The repeating number of the alkylene glycol group may be 100 or less, 50 or less, or 30 or less. The number of carbon atoms in the alkylene glycol group is preferably 2 or more and preferably 5 or less.

Examples of the polyalkylene glycol diglycidyl ether include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly1,4-butylene glycol diglycidyl ether, and the like.

From the viewpoint of improving the coating properties of the resin composition, the viscosity of the polyalkylene glycol diglycidyl ether at 25°C is preferably 100 MPa･s or more. From the viewpoint of improving workability, the viscosity of the polyalkylene glycol diglycidyl ether at 25°C is preferably 1000 MPa･s or less, more preferably 800 MPa･s or less, and further preferably 500 MPa･s or less. MPa･s or less.

The viscosity of the above-mentioned polyalkylene glycol diglycidyl ether can be measured, for example, using a B-type viscometer under the conditions of 25°C and 10 rpm. Examples of the above-mentioned B-type viscometer include "TVB-10 type" manufactured by Toki Industrial Co., Ltd.

The epoxy equivalent of the above-mentioned flexible epoxy resin is preferably 300 g/eq or more, more preferably 350 g/eq or more, further preferably 450 g/eq or more, and more preferably 1500 g/eq or less, more preferably It is preferably 1000 g/eq or less, more preferably 750 g/eq or less, and particularly preferably 500 g/eq or less. If the epoxy equivalent of the flexible epoxy resin is at least the above lower limit and below the above upper limit, the flexibility of the obtained cured product can be further improved.

The epoxy equivalent of the above-mentioned flexible epoxy resin can be measured according to JIS K7236:2001.

From the viewpoint of improving the mechanical strength of the obtained cured product, the thermosetting resin preferably contains the flexible epoxy resin and a thermosetting resin other than the flexible epoxy resin. Thermosetting resins other than the above-mentioned flexible epoxy resin preferably have no flexibility. Examples of thermosetting resins other than the above-described flexible epoxy resins include epoxy resins having a bisphenol skeleton, epoxy resins having a dicyclopentadiene skeleton, epoxy resins having a naphthalene skeleton, and adamantane skeletons. Epoxy resin with skeleton, epoxy resin with fluorine skeleton, epoxy resin with biphenyl skeleton, epoxy resin with bis(glycidyloxyphenyl)methane skeleton, epoxy resin with 𠮿 Epoxy resins with skeletons, epoxy resins with anthracene skeletons, epoxy resins with pyrene skeletons, and their hydrogenated products or modified products, etc. From the viewpoint of improving the mechanical strength of the obtained cured product, the thermosetting resin other than the above-mentioned flexible epoxy resin is preferably an epoxy resin containing a bisphenol skeleton.

From the viewpoint of improving the mechanical strength of the obtained cured product, the epoxy equivalent of the thermosetting resin other than the above-mentioned flexible epoxy resin is preferably 100 g/eq or more, more preferably 150 g/eq or more, and It is preferably 350 g/eq or less, more preferably 250 g/eq or less.

In 100% by weight of the above-mentioned resin composition, the content of the above-mentioned thermosetting resin is preferably 5% by weight or more, more preferably 7% by weight or more, and preferably 30% by weight or less, more preferably 15% by weight or less. If the content of the thermosetting resin is equal to or higher than the lower limit, the flexibility of the obtained cured product will be further increased. If the content of the thermosetting resin is below the upper limit, the heat dissipation properties of the obtained cured product can be further improved. In addition, when the above-mentioned resin composition contains two or more kinds of the above-mentioned thermosetting resins, the content of the above-mentioned thermosetting resins represents the total content of each thermosetting resin.

In 100% by weight of the above-mentioned resin composition, the content of the above-mentioned flexible epoxy resin is preferably 3% by weight or more, more preferably 5% by weight or more, and preferably 30% by weight or less, more preferably 15% by weight or less. . If the content of the flexible epoxy resin is equal to or higher than the lower limit, the flexibility of the obtained cured product can be further improved. If the content of the flexible epoxy resin is below the upper limit, the coating properties of the resin composition can be further improved. In addition, when the above-mentioned resin composition contains two or more kinds of the above-mentioned flexible epoxy resins, the content of the above-mentioned flexible epoxy resins represents the total content of each flexible epoxy resin.

In 100% by weight of the above-mentioned epoxy resin, the content of the above-mentioned flexible epoxy resin is preferably 30% by weight or more, more preferably 40% by weight or more, further preferably 50% by weight or more, and more preferably 90% by weight or less, more preferably 85% by weight or less. If the content of the flexible epoxy resin is equal to or higher than the lower limit, the flexibility of the obtained cured product can be further improved. If the content of the flexible epoxy resin is below the upper limit, the coating properties of the resin composition can be further improved. In addition, when the said epoxy resin contains two or more types of said flexible epoxy resins, the content of the said flexible epoxy resin means the total content of each flexible epoxy resin.

In 100% by weight of the above-mentioned flexible epoxy resin, the content of the above-mentioned polyalkylene glycol diglycidyl ether is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 50% by weight or more. In addition, the content is preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight or less. If the content of the polyalkylene glycol diglycidyl ether is not less than the above lower limit, the flexibility of the obtained cured product can be further improved. If the content of the polyalkylene glycol diglycidyl ether is below the upper limit, the coating properties of the resin composition can be further improved.

(Insulating filler) Insulating filler has insulating properties. Furthermore, insulation means that the volume resistivity of the filler is 10 ¹⁰ Ω･cm or more.

The above-mentioned insulating filler may be an organic filler or an inorganic filler. From the viewpoint of further improving the heat dissipation properties of the obtained hardened material, the insulating filler is preferably an inorganic filler. Only one type of the above-mentioned insulating filler may be used, or two or more types may be used in combination.

The maximum particle size of the above-mentioned insulating filler is 45 μm or less. Since the resin composition of the present invention has the above-mentioned structure, it can be applied to a substrate or the like in a thin layer, and the heat dissipation properties of the obtained cured product can be improved. From the viewpoint of coating the substrate and the like thinly, curing at low temperature and in a short time, and further improving the heat dissipation properties of the obtained cured product, the maximum particle size of the insulating filler is preferably 30 μm or less, and more preferably 25 μm or less, more preferably 20 μm or less, particularly preferably 10 μm or less. The lower limit of the maximum particle size of the insulating filler is not particularly limited. The maximum particle size of the above-mentioned insulating filler may be 10 μm or more, or may be 20 μm or more.

Furthermore, when the above-mentioned insulating filler includes two or more types of insulating fillers with different average particle diameters, the maximum particle diameter of the above-mentioned insulating filler refers to the maximum particle diameter of all insulating fillers.

The maximum particle size of the insulating filler can be determined, for example, by measuring the laser diffraction particle size distribution of the resin composition or a cured product of the resin composition. Specifically, the maximum particle size of the above-mentioned insulating filler is calculated by calculating the particle size (D100) of the insulating filler when the cumulative volume of the insulating filler is 100% (D100) from the particle size distribution based on the volume of the insulating filler. maximum particle size). Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by HORIBA Corporation. As the cured product of the above-mentioned resin composition, the cured product of the above-mentioned resin composition can be used. The cured product of the above-mentioned resin composition is obtained, for example, by heating the above-mentioned resin composition at 150° C. for 2 hours and hardening it. Furthermore, the thickness of the hardened material is not particularly limited. The thickness of the hardened material may be 5 μm or more, 10 μm or more, 100 μm or more, 500 μm or less, or 250 μm or less.

From the viewpoint of further improving the heat dissipation properties of the obtained hardened material, the average particle diameter of the insulating filler is preferably 0.2 μm or more, more preferably 4 μm or more, and preferably 45 μm or less, more preferably 25 μm or more. μm or less, more preferably 20 μm or less, particularly preferably 10 μm or less.

The average particle diameter of the insulating filler is preferably a number average particle diameter. The average particle size of the above-mentioned insulating filler is determined, for example, by observing any 50 insulating fillers with an electron microscope or an optical microscope and calculating the average particle size of each insulating filler, or by performing a laser diffraction particle size analysis. Distribution determination.

From the viewpoint of further improving the heat dissipation properties of the obtained hardened material and improving the filling properties, it is preferable that the volume-based particle size distribution of the above-mentioned insulating filler be in a region with a particle diameter of 0.1 μm or more and less than 1.0 μm. There is a peak in the region where the particle size is from 1.0 μm to 10 μm.

In addition, the peak existing in the region where the particle diameter is 0.1 μm or more and less than 1.0 μm refers to the peak whose particle diameter at the peak top is 0.1 μm or more and less than 1.0 μm. Peaks that exist in the region with a particle diameter of 1.0 μm or more and 10 μm or less refer to peaks whose particle diameter at the top of the peak is 1.0 μm or more and 10 μm or less.

From the viewpoint of further improving the heat dissipation properties of the obtained hardened material and improving the filling properties, the above-mentioned peak existing in the region where the particle diameter is 0.1 μm or more and less than 1.0 μm (first peak) is the same as the above-mentioned peak existing in the particle diameter. Among the peaks (second peak) in the region with a diameter of 1.0 μm or more and 10 μm or less, it is preferable that the second peak has a higher peak height.

In the volume-based particle size distribution of the above-mentioned insulating filler, there may be 2 peaks, more than 2 peaks, 3 or more peaks, 4 or more peaks, or 100 peaks. For the following peaks, there may also be less than 10 peaks. From the viewpoint of further improving the heat dissipation properties of the obtained hardened material and improving the filling properties, it is preferable that the volume-based particle size distribution of the insulating filler has two peaks. In order to adjust to the above-mentioned preferred aspect, the above-mentioned insulating filler may also include two or more types of insulating fillers with different average particle sizes.

In the volume-based particle size distribution of the insulating filler, the particle size (D50) of the insulating filler is preferably 20 μm or less, more preferably 10 μm or less. The particle size (D50) of the above-mentioned insulating filler is preferably 0.2 μm or more. If the particle diameter (D50) of the insulating filler is equal to or greater than the above lower limit, the effects of the present invention can be exerted more effectively.

Furthermore, the particle size (D50) of the above-mentioned insulating filler is the particle size of the insulating filler when the cumulative volume of the insulating filler is 50% in the volume-based particle size distribution of the above-mentioned insulating filler.

The coefficient of variation (CV value) of the particle size of the insulating filler is preferably 5% or more, more preferably 10% or more, and preferably 40% or less, more preferably 30% or less. If the variation coefficient of the particle diameter of the insulating filler is not less than the above lower limit and not more than the above upper limit, the heat dissipation properties of the obtained hardened material can be further improved. However, the CV value of the particle size of the above-mentioned insulating filler may be less than 5%.

The coefficient of variation (CV value) can be measured as follows. CV value (%)=(ρ/Dn)×100 ρ: standard deviation of particle size of insulating filler Dn: average particle size of insulating filler

The above-mentioned insulating filler may be in a spherical shape, may be in a shape other than a spherical shape, or may be in a flat shape. From the viewpoint of exerting the effects of the present invention more effectively, the shape of the insulating filler is preferably spherical.

From the viewpoint of further improving the heat dissipation properties of the obtained hardened material, the thermal conductivity of the insulating filler is preferably 10 W/m･K or more, more preferably 15 W/m･K or more, and still more preferably 20 W/m･K or more. The upper limit of the thermal conductivity of the insulating filler is not particularly limited. Inorganic fillers with thermal conductivity of approximately 300 W/m･K are well known, and inorganic fillers with thermal conductivity of approximately 200 W/m･K are easily available.

The above-mentioned insulating filler is preferably made of aluminum oxide, aluminum hydroxide, synthetic magnesite, magnesium hydroxide, diamond, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide. Moreover, the material of the above-mentioned insulating filler is more preferably alumina, synthetic magnesite, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide, and further preferably alumina. By using these preferred insulating fillers, the heat dissipation properties of the obtained hardened material can be further improved.

In 100% by weight of the above-mentioned resin composition, the content of the above-mentioned insulating filler is preferably 25% by weight or more, more preferably 50% by weight or more, further preferably 65% by weight or more, particularly preferably 70% by weight or more, and particularly preferably 80% by weight or more, preferably 93% by weight or less, more preferably 88% by weight or less. If the content of the insulating filler is at least the above lower limit and below the above upper limit, the heat dissipation properties of the obtained cured material can be further improved.

(heat hardener) The above-mentioned resin composition may contain a thermosetting agent. The above-mentioned resin composition preferably contains a thermosetting agent.

The thermosetting agent is not particularly limited. As the above-mentioned thermosetting agent, a suitable thermosetting agent capable of hardening a thermosetting resin can be used. In addition, in this specification, the above-mentioned thermosetting agent includes a hardening catalyst. Only one type of the above-mentioned thermosetting agent may be used, or two or more types may be used in combination.

From the viewpoint of further improving the heat resistance of the obtained cured product, the thermal curing agent preferably has an aromatic skeleton or an alicyclic skeleton. The above-mentioned thermal hardener preferably contains an amine hardener (amine compound), imidazole hardener, phenol hardener (phenol compound) or an acid anhydride hardener (acid anhydride), and more preferably contains a phenol hardener (phenol compound) or an acid anhydride hardener. (anhydride). The acid anhydride hardener preferably contains an acid anhydride having an aromatic skeleton, a hydride of the acid anhydride, or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, a hydride of the acid anhydride, or a modified product of the acid anhydride. .

Examples of the above-mentioned amine hardener include dicyandiamide, imidazole compounds, diaminodiphenylmethane, diaminodiphenyl sulfide, and the like. From the viewpoint of further improving the adhesiveness of the obtained cured product, the amine curing agent is more preferably dicyandiamide or an imidazole compound. From the viewpoint of improving the storage stability of the resin composition, the thermosetting agent preferably contains a hardening agent with a melting point of 180° C. or higher.

Examples of the imidazole hardener include: 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methyl 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl 2-Undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl-symmetric trisulfide, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl symmetric tris(2) ,4-Diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl symmetric trisulfate, 2,4-Diamino-6-[2'- Methylimidazolyl-(1')]-ethyl symmetric tris-isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct Products, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc.

Examples of the phenol hardener include phenolic novolac, o-cresol novolak, p-cresol novolac, tert-butylphenol novolak, dicyclopentadienocresol, polyp-vinylphenol, bis- Phenol A type novolac, xylylene modified novolac, decahydronaphthalene modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl) base) methane, etc. From the viewpoint of further improving the softness and flame retardancy of the obtained cured product, a phenol resin having a melamine skeleton, a phenol resin having a trisulfide skeleton, or a phenol resin having an allyl group is preferred.

Examples of commercially available phenol hardeners include MEH-8000H, MEH-8005, MEH-8010, and MEH-8015 (all manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Mitsubishi Chemical Corporation), and LA-7052. , LA-7054, LA-7751, LA-1356 and LA-3018-50P (the above are all manufactured by DIC Company), and ELPC75, PS6313 and PS6492 (the above are all manufactured by Qunrong Chemical Company), etc.

Examples of the acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include: styrene/maleic anhydride copolymer, benzophenone tetracarboxylic dianhydride, and pyromellitic acid. Dianhydride, trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glyceryl bis(dehydrated trimellitic acid ester) monoacetate, ethylene glycol bis (dehydrated trimellitate), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, etc.

Commercially available products of the above-mentioned acid anhydride having an aromatic skeleton, a hydrogenated product of the acid anhydride or a modified product of the acid anhydride include: SMA Resin EF30, SMA Resin EF40, SMA Resin EF60 and SMA Resin EF80 (the above are all manufactured by Sartomer Japan Company), ODPA-M and PEPA (the above are all manufactured by MANAC Company), RIKACID MTA-10, RIKACID MTA-15, RIKACID TMTA, RIKACID TMEG-100, RIKACID TMEG-200, RIKACID TMEG-300, RIKACID TMEG- 500, RIKACID TMEG-S, RIKACID HT-1A, RIKACID MT-500, and RIKACID TDA-100 (the above are all manufactured by New Nippon Rika Co., Ltd.), and EPICLON B4400, EPICLON B650, and EPICLON B570 (the above are all manufactured by DIC) )wait.

The above-mentioned acid anhydride with an alicyclic skeleton, the hydride of the acid anhydride or the modified product of the acid anhydride is preferably an acid anhydride with a polyalicyclic skeleton, the hydride of the acid anhydride or the modified product of the acid anhydride, or by terpene An acid anhydride with an alicyclic skeleton obtained by the addition reaction of an olefinic compound and maleic anhydride, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride. By using these thermal curing agents, the flexibility, moisture resistance, and adhesiveness of the obtained cured product can be further improved.

Examples of the above-mentioned acid anhydride having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include: methylacetic acid anhydride, an acid anhydride having a dicyclopentadiene skeleton, or a modified product of the acid anhydride. wait.

Commercially available products of the acid anhydride having an alicyclic skeleton, a hydrogenated product of the acid anhydride, or a modified product of the acid anhydride include: RIKACID MH-700, RIKACID HH, RIKACID TH, RIKACID DDSA, RIKACID OSA, and RIKACID HNA. and RIKACID HNA-100 (the above are all manufactured by New Nippon Rika Corporation), and EPI-CURE YH306, EPI-CURE YH307, EPI-CURE YH308H and EPI-CURE YH309 (the above are all manufactured by Mitsubishi Chemical Corporation), etc.

The above-mentioned thermal hardener is also preferably methylpyridine anhydride or trialkyl tetrahydrophthalic anhydride. By using methyl tetrahydrophthalic anhydride or trialkyl tetrahydrophthalic anhydride, the water resistance of the obtained hardened material becomes high.

In the above-mentioned resin composition, the above-mentioned thermal hardener is preferably a polymer containing a butadiene compound. The polymer of the above-mentioned butadiene compound may be a homopolymer of the butadiene compound, or may be a copolymer of the butadiene compound and a compound copolymerizable with the above-mentioned butadiene compound. From the viewpoint of exhibiting the effects of the present invention more effectively, the polymer of the butadiene compound is preferably a copolymer of the butadiene compound and a compound copolymerizable with the butadiene compound.

The butadiene compound is not particularly limited. Examples of the butadiene compound include butadiene, isoprene, and the like.

Examples of compounds copolymerizable with the above-mentioned butadiene compound include maleic acid, maleic anhydride, alcohol, amine compounds, acrylic esters, acrylonitrile, and styrene. Examples of the amine compound include diamines and the like. From the viewpoint of further favorably hardening the epoxy resin, the compound copolymerizable with the butadiene compound is preferably maleic acid or maleic anhydride, and more preferably maleic anhydride.

The polymer of the above-mentioned butadiene compound preferably has two or more functional groups (reactive groups) that can react with the thermosetting functional group of the above-mentioned thermosetting resin, and preferably has two or more functional groups that can react with the above-mentioned epoxy resin. Functional group (reactive group) for epoxy reaction. The number of the reactive groups per molecule in the polymer of the butadiene compound is preferably 2 or more. From the viewpoint of hardening the resin composition at low temperature and in a short time, the number of the reactive groups per molecule in the polymer of the butadiene compound is preferably 2 or more, more preferably 3 or more, and still more preferably It is 4 or more, particularly preferably 5 or more, more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less.

The number of the above-mentioned reactive groups in the polymer of the above-mentioned butadiene compound can be adjusted to a preferred range by adjusting the mixing ratio of the butadiene compound and the compound having the above-mentioned reactive groups.

Examples of the functional group (reactive group) that can react with the epoxy group of the epoxy resin include groups having a carbon-carbon unsaturated bond such as vinyl groups, hydroxyl groups, glycidyl groups, isocyanato groups, and amines. group, carboxyl group and acid anhydride group, etc. From the viewpoint of hardening the resin composition at low temperature and in a short time, the reactive group in the polymer of the butadiene compound preferably contains a hydroxyl group or an acid anhydride group, and more preferably contains an acid anhydride group.

From the viewpoint of hardening the resin composition at low temperature and in a short time, the equivalent of the reactive group in the polymer of the butadiene compound is preferably 300 g/eq or more, more preferably 450 g/eq or more. , and preferably below 1500 g/eq, more preferably below 1000 g/eq.

The equivalent of the reactive group in the polymer of the butadiene compound can be measured by potentiometric titration, indicator titration, or the like.

The homopolymer of the above-mentioned butadiene compound can be obtained by polymerizing the butadiene compound. Furthermore, the copolymer of the above-mentioned butadiene compound and the compound copolymerizable with the above-mentioned butadiene compound can be obtained by copolymerizing the butadiene compound and the compound copolymerizable with the above-mentioned butadiene compound. Examples of the above-mentioned polymerization method include known methods such as radical polymerization, ionic polymerization, condensation polymerization (polycondensation), addition condensation, living polymerization, and living radical polymerization. Moreover, as another polymerization method, suspension polymerization in the presence of a radical polymerization initiator can be mentioned.

The viscosity of the above-mentioned thermal hardener at 25°C is preferably above 100 MPa･s, more preferably above 300 MPa･s, further preferably above 500 MPa･s, and preferably below 10000 MPa･s, and more preferably Preferably, it is below 1000 MPa･s. If the viscosity of the thermosetting agent at 25°C is above the above lower limit and below the above upper limit, the coating properties of the resin composition can be further improved.

In 100% by weight of the resin composition, the content of the thermosetting agent is preferably 0.1% by weight or more, more preferably 3% by weight or more, and preferably 40% by weight or less, more preferably 25% by weight or less. If the content of the thermosetting agent is equal to or higher than the lower limit, the resin composition can be sufficiently hardened easily. If the content of the thermosetting agent is below the upper limit, it will be difficult to generate excess thermosetting agent that does not participate in hardening. Therefore, the heat resistance and adhesiveness of the obtained hardened material become high.

The content of the thermosetting agent is preferably 0.1 parts by weight or more, more preferably 50 parts by weight or more, and preferably 100 parts by weight or less based on 100 parts by weight of the thermosetting resin. If the content of the thermosetting agent is equal to or higher than the lower limit, the resin composition can be sufficiently hardened easily. If the content of the thermosetting agent is below the upper limit, it will be difficult to generate excess thermosetting agent that does not participate in hardening. Therefore, the heat resistance and adhesiveness of the obtained hardened material become high.

The content of the polymer of the above-mentioned butadiene compound in the above-mentioned thermosetting agent is preferably 25 parts by weight or more, more preferably 50 parts by weight or more, and preferably 150 parts by weight or less, relative to 100 parts by weight of the above-mentioned thermosetting resin. More preferably, it is 100 parts by weight or less. If the content of the polymer of the butadiene compound in the thermosetting agent is equal to or higher than the lower limit, the resin composition can be hardened at low temperature and in a short time. If the content of the polymer of the butadiene compound in the thermosetting agent is less than the upper limit, it will be difficult to generate excess thermosetting agent that does not participate in curing. Therefore, the heat resistance and adhesiveness of the obtained hardened material become high.

The content of the polymer of the above-mentioned butadiene compound in the above-mentioned thermal hardener is preferably 25 parts by weight or more, more preferably 50 parts by weight or more, and preferably 150 parts by weight or less relative to 100 parts by weight of the above-mentioned epoxy resin. , more preferably 100 parts by weight or less. If the content of the polymer of the butadiene compound in the thermosetting agent is equal to or higher than the lower limit, the resin composition can be hardened at low temperature and in a short time. If the content of the polymer of the butadiene compound in the thermosetting agent is less than the upper limit, it will be difficult to generate excess thermosetting agent that does not participate in curing. Therefore, the heat resistance and adhesiveness of the obtained hardened material become high.

(dispersant) The above-mentioned resin composition may further contain a dispersant. From the viewpoint of improving the dispersibility of the obtained cured product, the resin composition preferably further contains a dispersant.

Examples of the dispersant include polycarboxylates, alkylammonium salts, hydroxyalkylammonium salts, phosphate ester salts, acrylic block copolymers, and polymer salts. Only one type of the above-mentioned dispersing agent may be used, or two or more types may be used in combination.

From the viewpoint of improving the dispersibility of the obtained cured product, the dispersant is preferably a polycarboxylate, a hydroxyalkylammonium salt, or a phosphate ester salt.

From the viewpoint of improving the dispersibility of the obtained hardened product, the amine value of the dispersant is preferably 40 KOHmg/g or more, more preferably 50 KOHmg/g or more, and more preferably 95 KOHmg/g or less. Preferably it is below 85 KOHmg/g. In addition, the amine value of the said dispersing agent can be measured based on JIS K7237.

From the viewpoint of improving the dispersibility of the insulating filler, the acid value of the dispersant is preferably 45 KOHmg/g or more, more preferably 50 KOHmg/g or more, and more preferably 95 KOHmg/g or less, more preferably 85 KOHmg/g or less. In addition, the acid value of the above-mentioned dispersant can be measured in accordance with JIS K0070.

From the viewpoint of improving the dispersibility of the insulating filler, the amine value of the dispersant is preferably 40 KOHmg/g or more and 95 KOHmg/g or less, and the acid value of the dispersant is preferably 45 KOHmg/g or more and 95 KOHmg/g. the following.

From the viewpoint of improving the dispersibility of the insulating filler, the absolute value of the difference between the amine value of the dispersant and the acid value of the dispersant is preferably 10 KOHmg/g or less, more preferably 7 KOHmg/g or less. The lower limit of the absolute value of the difference between the amine value of the dispersant and the acid value of the dispersant is not particularly limited. The absolute value of the difference between the amine value of the dispersant and the acid value of the dispersant may also be 0 KOHmg/g (the amine value and the acid value are the same).

In 100% by weight of the resin composition, the content of the dispersant is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and preferably 2% by weight or less, more preferably 1% by weight or less. If the content of the dispersant is equal to or greater than the lower limit and equal to or less than the upper limit, the dispersibility of the insulating filler becomes higher.

(other ingredients) In addition to the above-mentioned components, the above-mentioned resin composition may also contain chelating agents, antioxidants, ion trapping agents, storage stabilizers, anti-aging agents, etc.

(semiconductor device) The semiconductor device of the present invention includes a substrate, a die adhesive material arranged on the surface of the substrate, and a semiconductor element (wafer) arranged on the surface of the die adhesive material. In the semiconductor device of the present invention, the die adhesive material is a cured product of a resin composition including a thermosetting resin and an insulating filler. In the semiconductor device of the present invention, the maximum particle size of the insulating filler is 45 μm or less. In the semiconductor device of the present invention, the die adhesive material is a cured product of the above-mentioned resin composition.

The cured product of the above-mentioned resin composition is obtained, for example, by heating the above-mentioned resin composition at 150° C. for 2 hours and hardening it. Furthermore, the thickness of the hardened material is not particularly limited. The thickness of the above-mentioned hardened material may be 5 μm or more, 10 μm or more, or 20 μm or more. In addition, the thickness of the hardened material may be 500 μm or less, 100 μm or less, or 25 μm or less.

FIG. 1 is a cross-sectional view schematically showing a semiconductor device using a cured product of the resin composition according to the first embodiment of the present invention.

The semiconductor device 1 shown in FIG. 1 includes a substrate 2, a die attach material 3 disposed on the surface of the substrate 2, and a semiconductor element 4 disposed on the surface of the die attach material 3 opposite to the substrate 2 side. The die attach material 3 is formed by hardening the above-mentioned resin composition. The die attach material 3 is a cured product of a resin composition including a thermosetting resin and an insulating filler 3A. The maximum particle size of insulating filler 3A is 45 μm or less. Furthermore, in Figure 1, for convenience of illustration, the size and thickness are different from the actual size.

In addition, the structure shown in FIG. 1 is only an example of a semiconductor device, and the arrangement structure of the hardened|cured material of a resin composition, etc. can be suitably modified.

The above-mentioned substrate is not particularly limited. Examples of the above-mentioned substrate include a glass substrate, a glass epoxy substrate, a flexible printed substrate, a metal substrate, a polyimide substrate, and the like.

The above-mentioned semiconductor element is not particularly limited. Examples of the semiconductor element include optical semiconductor elements, solid-state imaging elements, and the like. Examples of the optical semiconductor element include a light emitting diode (LED) chip and the like. Examples of the solid-state imaging element include a CCD sensor, a CMOS sensor, and the like. The above-mentioned semiconductor element is preferably a CMOS sensor. The above resin composition is suitable for CMOS sensors.

Hereinafter, the present invention will be clarified by citing specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

Prepare the following materials.

(insulating filler) Alumina A ("AA05" manufactured by Sumitomo Chemical Co., Ltd., has an average particle size of 0.5 μm, a particle size (D90) of 1.0 μm, a particle size (D100) of 1.4 μm, a specific gravity of 3.8, and a thermal conductivity of 32 W/m ･K) Alumina B ("AA3" manufactured by Sumitomo Chemical Co., Ltd., has an average particle size of 3.5 μm, a particle size (D90) of 6.0 μm, a particle size (D100) of 8.0 μm, a specific gravity of 3.8, and a thermal conductivity of 32 W/m ･K) Alumina C ("AS50" manufactured by Showa Denko Co., Ltd., has an average particle size of 10 μm, a particle size (D90) of 25 μm, a particle size (D100) of 30 μm, a specific gravity of 3.8, and a thermal conductivity of 32 W/m ･K) Alumina D ("AS30" manufactured by Showa Denko Co., Ltd., has an average particle size of 18 μm, a particle size (D90) of 40 μm, a particle size (D100) of 45 μm, a specific gravity of 3.8, and a thermal conductivity of 32 W/m ･K) Alumina 1 ("AL35-75" manufactured by Micron Corporation, the average particle size is 40 μm, the particle size (D90) is 85 μm, the particle size (D100) is 90 μm, the specific gravity is 3.8, and the thermal conductivity is 32 W/ m･K)

(Thermosetting resin) Flexible epoxy resin: Epoxy resin A (polyethylene oxide modified bisphenol A type epoxy resin, "EP4003S" manufactured by ADEKA, epoxy equivalent is 470 g/eq, viscosity at 25°C is 1600 MPa･s) Epoxy resin B (polyalkylene glycol diglycidyl ether, "RD119LE" manufactured by Aditya Company, the number of repeats of alkylene glycol groups is 8, the epoxy equivalent is 310 g/eq, at 25°C Viscosity: 80 MPa･s) Epoxy resin C (polyalkylene glycol diglycidyl ether, "EX991" manufactured by Nagase chemteX Co., Ltd., the repeat number of alkylene glycol groups is 10, the epoxy equivalent is 450 g/eq, at 25°C The viscosity is 180 MPa･s) Epoxy resin D (polyalkylene glycol diglycidyl ether, "EPO-PEG-EPO 2K" manufactured by Nano soft polymers, the number of repeating alkylene glycol groups is 41, and the epoxy equivalent is 1000 g/ eq, the viscosity at 25℃ is 20000 MPa･s) Epoxy Resin E (Rubber modified epoxy resin, "EPR-2000" manufactured by ADEKA, epoxy equivalent is 215 g/eq, viscosity at 25°C is 23000 MPa･s) Thermosetting resins other than flexible epoxy resins: Epoxy resin 1 (bisphenol A type epoxy resin, "YD127" manufactured by Nippon Steel Chemical Material Co., Ltd., epoxy equivalent is 180 g/eq, viscosity at 25°C is 10000 MPa･s)

(heat hardener) Acid anhydride hardener A (an acid anhydride with an alicyclic skeleton, "RIKACID MH700" manufactured by Shinnippon Rika Co., Ltd., the equivalent of the reactive group (anhydride group) is 165 g/eq, liquid at 25°C, The viscosity is 100 MPa･s) Acid anhydride hardener B (an acid anhydride with an alicyclic skeleton, "RIKACID OSA" manufactured by Shinnippon Rika Co., Ltd., the equivalent of the reactive group (anhydride group) is 210 g/eq, it is liquid at 25°C, and it is liquid at 25°C The viscosity is 500 MPa･s) Acid anhydride hardener C (an acid anhydride with a branched long-chain dibasic acid skeleton, "IPU22AH" manufactured by Okamura Oil Co., Ltd., the equivalent of the reactive group (anhydride group) is 280 g/eq, and is liquid at 25°C. Viscosity at 25℃ is 1000 MPa･s) Phenol hardener A (phenolic novolac, "MEH8000H" manufactured by Meiwa Chemical Co., Ltd., the equivalent of the reactive group (phenol group) is 140 g/eq, it is liquid at 25°C, and the viscosity at 25°C is 1000 MPa ･s) Phenol hardener B (phenolic novolak, "MEH8005" manufactured by Meiwa Chemical Co., Ltd., the equivalent of the reactive group (phenol group) is 140 g/eq, it is liquid at 25°C, and the viscosity at 25°C is 10000 MPa ･s) Phenol hardener C (phenolic novolac, "ELPC75" manufactured by Qunrong Chemical Co., Ltd., the equivalent of the reactive group (phenol group) is 223 g/eq, it is liquid at 25°C, and the viscosity at 25°C is 20000 MPa･s) Polymer A of butadiene compound (copolymer of butadiene and maleic anhydride, the number of reactive groups (anhydride groups) per molecule is 2, the equivalent weight of the reactive groups is 635 g/eq, at 25°C The viscosity is 1000 MPa･s) Polymer B of butadiene compound (copolymer of butadiene and maleic anhydride, the number of reactive groups (anhydride groups) per molecule is 4, the equivalent weight of the reactive groups is 750 g/eq, at 25°C The viscosity is 30000 MPa･s) Polymer C of butadiene compound (copolymer of butadiene and maleic anhydride, the number of reactive groups (anhydride groups) per molecule is 4, the equivalent weight of the reactive groups is 1250 g/eq, at 25°C The viscosity is 50000 MPa･s) Butadiene compound polymer D (copolymer of butadiene and alcohol, the number of reactive groups (hydroxyl groups) per molecule is 4, the equivalent of the reactive groups is 1250 g/eq, and the viscosity at 25°C is 50000 MPa･s) Butadiene compound polymer E (copolymer of butadiene and maleic acid, the number of reactive groups (carboxyl groups) per molecule is 4, the equivalent of the reactive groups is 1250 g/eq, at 25°C Viscosity is 50000 MPa･s) Butadiene compound polymer F (copolymer of butadiene and diamine, the number of reactive groups (amine groups) per molecule is 4, the equivalent of the reactive groups is 1250 g/eq, at 25°C Viscosity: 50000 MPa･s) Polymer G of butadiene compound (copolymer of butadiene and maleic anhydride, the number of reactive groups (anhydride groups) per molecule is 5, the equivalent weight of the reactive groups is 600 g/eq, at 25°C The viscosity is 100000 MPa･s) Polymer H of butadiene compound (copolymer of butadiene and maleic anhydride, the number of reactive groups (anhydride groups) per molecule is 10, the equivalent weight of the reactive groups is 300 g/eq, at 25°C The viscosity is 50000 MPa･s) Polymer I of butadiene compound (the number of reactive groups (anhydride groups) per molecule is 15, the equivalent weight of the reactive groups is 150 g/eq, and the viscosity at 25°C is 50000 MPa･s)

(dispersant) Dispersant A (phosphate ester salt, "DISPERBYK145" manufactured by BYK Corporation, acid value: 76 KOHmg/g, amine value: 71 KOHmg/g) Dispersant B (phosphate ester salt, "DISPERBYK142" manufactured by BYK Corporation, acid value: 46 KOHmg/g, amine value: 43 KOHmg/g) Dispersant C (phosphate ester salt, "DISPERBYK111" manufactured by BYK Corporation, acid value: 129 KOHmg/g)

(catalyst) Catalyst ("HX3721" manufactured by Asahi Kasei Co., Ltd.)

(Examples 1 to 47 and Comparative Examples 1 to 5) The ingredients shown in Tables 1 to 28 below were mixed in the amounts shown in Tables 1 to 28 below to obtain a resin composition (grain adhesion paste).

(evaluation) (1) Particle size (D90) and particle size (D100) of insulating filler (maximum particle size) The obtained resin composition was subjected to laser diffraction particle size distribution measurement using a laser diffraction particle size distribution measuring device ("LA-960" manufactured by HORIBA Corporation). In the volume-based particle size distribution of the insulating filler, calculate the particle size (D90) of the insulating filler when the cumulative volume of the insulating filler is 90% and the particle size (D100) of the insulating filler when the cumulative volume is 100% ( maximum particle size).

(2)Viscosity The viscosity (Pa･s) of the obtained resin composition at 25°C and 10 rpm was measured using a B-type viscometer ("TVB-10 type" manufactured by Toki Industrial Co., Ltd.). Also, find the ratio (thixotropic index) of the viscosity at 25°C and 1 rpm to the viscosity at 25°C and 10 rpm.

(3) Storage modulus of hardened material As a substrate, "PET Film JP4020" manufactured by Reiko Co., Ltd. was prepared. The resin composition was coated on the surface of the above-mentioned substrate with a thickness of 500 μm using an applicator. Then, it was heated at 150° C. for 2 hours using a dryer to harden, and a test sample A (hardened material) of 20 mm×5 mm×500 μm in thickness was obtained. For the test sample A, a forced vibration type dynamic viscoelasticity measuring device ("DVA-200" manufactured by Japan IT Measurement Control Co., Ltd.) was used under tensile conditions, frequency 10 Hz, strain 0.1%, and temperature range 0°C to 150°C. , and a temperature rise rate of 2°C/min. The measured value is taken as the storage modulus at 25°C.

(4) Thermal conductivity of hardened material As a substrate, "PET Film JP4020" manufactured by Reiko Co., Ltd. was prepared. The resin composition was coated on the surface of the above-mentioned substrate with a thickness of 500 μm using an applicator. Then, it was heated at 150° C. for 2 hours using a dryer to harden, and a test sample B (hardened material) of 100 mm×100 mm×500 μm in thickness was obtained. The thermal conductivity of the test sample B was measured using a thermal conductivity meter ("Quick Thermal Conductivity Meter QTM-500" manufactured by Kyoto Electronics Industry Co., Ltd.).

(5)Softness Based on the storage modulus of the cured material measured in (3), the softness of the cured material is determined based on the following criteria.

[Criteria for judging softness] ○○: The storage modulus of the hardened material is 500 MPa or less ○: The storage modulus of the hardened material exceeds 500 MPa and is less than 1000 MPa △: The storage modulus of the hardened material exceeds 1000 MPa and is less than 2000 MPa ×: The storage modulus of the hardened material exceeds 2000 MPa

(6)Heat dissipation Using the thermal conductivity of the cured material measured in (4) and the coating thickness of the resin composition (25 μm), the thermal resistance of the cured material was calculated by the following formula. In addition, for a resin composition in which the maximum particle diameter of the insulating filler exceeds 25 μm, the maximum particle diameter of the insulating filler in each resin composition is defined as the coating thickness. The heat dissipation properties of the hardened material are judged based on the following criteria. Thermal resistance of hardened material (m･K･μm/W) = coating thickness of resin composition (μm)/thermal conductivity (W/m･K)

[Criteria for judging heat dissipation] ○○: The thermal resistance of the hardened object is less than 20 ○: The thermal resistance of the hardened material is 20 or more and less than 30 ×: The thermal resistance of the hardened material is 30 or more

(7) Inhibition of warpage The obtained resin composition was dispensed into a WX pattern (12 mm × 9 mm) on a copper substrate, a silicon wafer (12 mm × 9 mm) was mounted on it, and pressed with a pressure of 0.3 MPa for crimping. Then, it was heated at 150° C. for 2 hours to harden, thereby obtaining a structure having a cured product of the resin composition. Then, while heating the bottom surface of the above structure from 25°C to 80°C with a heating plate at a heating rate of 5°C/min, the warp height at 25°C was measured with a laser microscope every 5 minutes (KEYENCE company), measure the maximum height of warpage. Furthermore, the coating thickness of the resin composition is 25 μm. For resin compositions in which the maximum particle size of the insulating filler used exceeds 25 μm, the maximum particle size of the insulating filler in each resin composition is set as the coating thickness. cloth thickness. In addition, in Comparative Example 1 in which the maximum particle diameter of the insulating filler exceeds 45, the resin composition cannot be applied thinly, so the warpage test was not performed. The warpage suppression performance is judged based on the following criteria.

[Criteria for judging warpage resistance] ○○：The height of warpage is 3 μm or less ○：The height of warpage exceeds 3 μm and is less than 6 μm △: The height of warpage exceeds 6 μm and is less than 9 μm ×: Warpage height exceeds 9 μm and is less than 12 μm ××: The height of warpage exceeds 12 μm

(8) Low temperature rapid hardening property Use an applicator to apply the resin composition to a thickness of 50 μm on the surface of the substrate. Then, it was heated at 150° C. for 15 minutes using a dryer to harden, and a test sample C (hardened material) of 100 mm×100 mm×50 μm in thickness was obtained. Then, the test sample C was crushed with a mortar to obtain a crushed product. The obtained crushed material was subjected to a differential scanning calorimetry (DSC) device ("EXSTAR DSC7020" manufactured by SII Corporation) in a nitrogen atmosphere in the range of -50°C to 150°C and a temperature rise rate of 5°C/min. Determine the exothermic peak area B of the broken material. The exothermic peak area A of the resin composition before curing is measured in the same manner. "Reaction rate (%) = (1 - (exothermic peak area B/exothermic peak area A)) × 100" was calculated, and the low-temperature rapid hardening property was determined based on the following criteria.

[Judgment criteria for low temperature rapid hardening properties] ○○：Reaction rate is over 95% ○: The response rate is more than 90% and less than 95% △: The response rate is more than 85% and less than 90% △△: The response rate is more than 75% and less than 85% ××: The response rate does not reach 75%

The composition and results are shown in Tables 1 to 28 below.

[Table 1] Example 1 Example 2 Example 3 Example 4 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% 0.8 0.8 Epoxy Resin B weight% 6.0 Epoxy Resin C weight% 6.0 6.0 6.8 Epoxy Resin D weight% Epoxy Resin E weight% 0.8 Epoxy resin 1 weight% 1.7 1.7 1.7 1.7 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 80.0 heat hardener Acid anhydride hardener A weight% Acid anhydride hardener B weight% 5.9 5.9 5.9 5.9 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol Hardener B weight% Phenol hardener C weight% dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 Dispersant B weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 2] Example 1 Example 2 Example 3 Example 4 hardened matter Store modulus MPa 500 390 380 360 thermal conductivity W/m･K 2.1 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 30 40 50 50 thixotropic index - 2.5 2.5 3.0 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 11.90 Low temperature rapid hardening - △△ △△ △△ △△ Softness - 〇〇 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 6.0 5.0 5.0 4.0 determination - 〇 〇 〇 〇

[table 3] Example 5 Example 6 Example 7 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% 3.4 Epoxy Resin B weight% 3.4 Epoxy Resin C weight% 3.0 3.4 Epoxy Resin D weight% 3.8 Epoxy Resin E weight% 3.4 Epoxy resin 1 weight% 1.7 1.7 1.7 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 heat hardener Acid anhydride hardener A weight% Acid anhydride hardener B weight% 5.9 5.9 5.9 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol Hardener B weight% Phenol hardener C weight% dispersant Dispersant A weight% 0.5 0.5 0.5 Dispersant B weight% catalyst weight% 0.1 0.1 0.1

[Table 4] Example 5 Example 6 Example 7 hardened matter Store modulus MPa 300 450 800 thermal conductivity W/m･K 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 60 50 100 thixotropic index - 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 Low temperature rapid hardening - △△ △△ △△ Softness - 〇〇 〇〇 〇 Heat dissipation - 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 3.0 6.0 7.0 determination - 〇〇 〇 △

[table 5] Example 8 Example 9 Example 10 Example 11 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% 6.8 6.8 6.8 6.8 Epoxy Resin C weight% Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.7 1.7 1.7 1.7 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 80.0 heat hardener Acid anhydride hardener A weight% 5.9 Acid anhydride hardener B weight% Acid anhydride hardener C weight% 5.9 Phenol hardener A weight% 5.9 Phenol Hardener B weight% 5.9 Phenol hardener C weight% dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 Dispersant B weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 6] Example 8 Example 9 Example 10 Example 11 hardened matter Store modulus MPa 550 400 410 450 thermal conductivity W/m･K 2.1 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 45 45 60 70 thixotropic index - 2.5 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 11.90 Low temperature rapid hardening - △△ △△ △△ △△ Softness - 〇 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 7.0 5.0 6.0 6.0 determination - △ 〇 〇 〇

[Table 7] Example 12 Example 13 Example 14 Example 15 Resin composition Insulating filler Alumina A weight% 20.0 20.0 28.0 30.0 Alumina B weight% 55.0 60.0 60.0 63.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% 5.4 4.3 2.6 1.5 Epoxy Resin B weight% Epoxy Resin C weight% 6.0 4.8 2.9 1.7 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 2.9 2.3 1.4 0.8 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 80.0 heat hardener Acid anhydride hardener A weight% Acid anhydride hardener B weight% 9.8 7.8 4.7 2.7 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol hardener B weight% Phenol Hardener C weight% dispersant Dispersant A weight% 0.8 0.7 0.4 0.2 Dispersant B weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 8] Example 12 Example 13 Example 14 Example 15 hardened matter Store modulus MPa 300 330 500 700 thermal conductivity W/m･K 1.0 1.5 2.3 4.0 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 35 50 60 85 thixotropic index - 2.0 2.1 3.2 3.3 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 25.00 16.67 10.87 6.25 Low temperature rapid hardening - △△ △△ △△ △△ Softness - 〇〇 〇〇 〇〇 〇 Heat dissipation - 〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 6.0 5.0 4.0 3.0 determination - 〇 〇 〇 〇〇

[Table 9] Example 16 Example 17 Example 18 Example 19 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 Alumina C weight% 60.0 Alumina D weight% 60.0 Alumina 1 weight% Particle size (D90) μm 25.0 40.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 30.0 45.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 6.8 6.8 3.0 5.0 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.7 1.7 7.0 5.0 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 30.0 50.0 heat hardener Acid anhydride hardener A weight% 4.4 4.4 Acid anhydride hardener B weight% 5.9 5.9 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol hardener B weight% Phenol hardener C weight% dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 Dispersant B weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 10] Example 16 Example 17 Example 18 Example 19 hardened matter Store modulus MPa 350 350 2000 1500 thermal conductivity W/m･K 2.1 2.2 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 60 60 150 150 thixotropic index - 2.0 1.8 2.5 2.5 Coating thickness of resin composition μm 30.0 45.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 14.29 20.45 11.90 11.90 Low temperature rapid hardening - △△ △△ △△ △△ Softness - 〇〇 〇〇 △ △ Heat dissipation - 〇〇 〇 〇〇 〇〇 Inhibition of warpage warp height μm 4.0 6.0 9.0 8.0 determination - 〇 〇 △ △

[Table 11] Example 20 Example 21 Resin composition Insulating filler Alumina A weight% 25.0 25.0 Alumina B weight% 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 thermosetting resin Epoxy Resin A weight% 8.0 Epoxy Resin B weight% Epoxy Resin C weight% 6.8 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.7 0.5 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 94.1 heat hardener Acid anhydride hardener A weight% Acid anhydride hardener B weight% 5.9 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol hardener B weight% Phenol hardener C weight% 5.9 dispersant Dispersant A weight% 0.5 Dispersant B weight% 0.5 catalyst weight% 0.1 0.1

[Table 12] Example 20 Example 21 hardened matter Store modulus MPa 1500 700 thermal conductivity W/m･K 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 150 200 thixotropic index - 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 Thermal resistance of hardened material m･K･ μm/W 11.90 11.90 Low temperature rapid hardening - × × Softness - △ 〇 Heat dissipation - 〇〇 〇〇 Inhibition of warpage warp height μm 8.0 8.0 determination - △ △

[Table 13] Example 22 Example 23 Example 24 Example 25 Example 26 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 6.3 6.3 6.3 6.3 1.0 Epoxy Resin D weight% 5.3 Epoxy Resin E weight% Epoxy resin 1 weight% 1.6 1.6 1.6 1.6 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 80.0 79.9 heat hardener Butadiene compound polymer A weight% 6.0 Butadiene compound polymer B weight% 6.0 Butadiene compound polymer C weight% Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% 6.0 Butadiene compound polymer H weight% 6.0 Butadiene compound polymer I weight% 6.0 Acid anhydride hardener A weight% 0.5 0.5 0.5 0.5 0.5 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 75.9 75.9 75.9 76.1 dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1 0.1 0.1

[Table 14] Example 22 Example 23 Example 24 Example 25 Example 26 hardened matter Store modulus MPa 360 300 370 400 500 thermal conductivity W/m･K 2.1 2.1 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 60 70 85 80 80 thixotropic index - 2.5 3.0 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 11.90 11.90 Low temperature rapid hardening - 〇 〇 〇〇 〇〇 〇〇 Softness - 〇〇 〇〇 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 4.00 4.00 4.00 5.00 6.00 determination - 〇 〇 〇 〇 〇

[Table 15] Example 27 Example 28 Example 29 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 4.2 7.0 8.3 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.0 1.7 2.1 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.1 80.0 heat hardener Butadiene compound polymer A weight% Butadiene compound polymer B weight% 7.8 4.3 2.6 Butadiene compound polymer C weight% Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 1.4 1.4 1.4 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 150.0 49.4 25.0 dispersant Dispersant A weight% 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1

[Table 16] Example 27 Example 28 Example 29 hardened matter Store modulus MPa 250 500 750 thermal conductivity W/m･K 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 150 80 60 thixotropic index - 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 Low temperature rapid hardening - 〇〇 〇 △ Softness - 〇〇 〇〇 〇 Heat dissipation - 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 2.00 6.00 7.00 determination - 〇〇 〇 △

[Table 17] Example 30 Example 31 Example 32 Example 33 Resin composition Insulating filler Alumina A weight% 20.0 20.0 28.0 30.0 Alumina B weight% 55.0 60.0 60.0 63.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 10.7 8.5 5.0 2.8 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 2.7 2.1 1.3 0.7 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 80.0 80.0 heat hardener Butadiene compound polymer A weight% Butadiene compound polymer B weight% 10.2 8.1 4.8 2.7 Butadiene compound polymer C weight% Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 0.8 0.7 0.4 0.2 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 75.9 75.9 75.9 dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 18] Example 30 Example 31 Example 32 Example 33 hardened matter Store modulus MPa 200 250 500 1000 thermal conductivity W/m･K 1.05 1.5 2.5 3.0 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 30 40 120 200 thixotropic index - 2.0 2.1 3.2 3.3 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 23.81 16.67 10.00 8.33 Low temperature rapid hardening - 〇 〇 〇 〇 Softness - 〇〇 〇〇 〇〇 〇 Heat dissipation - 〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 7.00 6.00 5.00 4.00 determination - △ 〇 〇 〇

[Table 19] Example 34 Example 35 Example 36 Example 37 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 Alumina B weight% Alumina C weight% 60.0 60.0 60.0 Alumina D weight% 60.0 Alumina 1 weight% Particle size (D90) μm 25.0 34.0 25.0 25.0 Particle size (D100) (maximum particle size) μm 30.0 45.0 30.0 30.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% 6.3 Epoxy Resin C weight% 6.3 6.3 Epoxy Resin D weight% 6.3 Epoxy Resin E weight% Epoxy resin 1 weight% 1.6 1.6 1.6 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 80.0 79.9 79.9 heat hardener Butadiene compound polymer A weight% Butadiene compound polymer B weight% 6.0 6.0 6.0 6.0 Butadiene compound polymer C weight% Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 0.5 0.5 0.5 0.5 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 75.9 76.1 76.1 dispersant Dispersant A weight% 0.5 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1 0.1

[Table 20] Example 34 Example 35 Example 36 Example 37 hardened matter Store modulus MPa 330 400 400 200 thermal conductivity W/m･K 2.3 2.4 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 55 50 80 80 thixotropic index - 2.3 2.0 2.0 2.0 Coating thickness of resin composition μm 30.0 45.0 30.0 30.0 Thermal resistance of hardened material m･K･μm/W 13.04 18.75 14.29 14.29 Low temperature rapid hardening - 〇 〇 △ △ Softness - 〇〇 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 5.00 6.00 6.00 2.00 determination - 〇 〇 〇 〇〇

[Table 21] Example 38 Example 39 Example 40 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 6.3 6.3 6.3 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.6 1.6 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 79.7 79.7 79.7 heat hardener Butadiene compound polymer A weight% 6.0 Butadiene compound polymer B weight% Butadiene compound polymer C weight% 6.0 Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% 6.0 Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 0.5 0.5 0.5 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 75.9 75.9 dispersant Dispersant A weight% 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1

[Table 22] Example 38 Example 39 Example 40 hardened matter Store modulus MPa 300 300 500 thermal conductivity W/m･K 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 60 150 200 thixotropic index - 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 Low temperature rapid hardening - 〇 〇 〇〇 Softness - 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 3.00 3.00 6.00 determination - 〇〇 〇〇 〇

[Table 23] Example 41 Example 42 Example 43 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 6.3 6.3 6.3 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.6 1.6 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 79.7 79.7 79.7 heat hardener Butadiene compound polymer A weight% Butadiene compound polymer B weight% Butadiene compound polymer C weight% Butadiene compound polymer D weight% 6.0 Butadiene compound polymer E weight% 6.0 Butadiene compound polymer F weight% 6.0 Butadiene compound polymer G weight% Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 0.5 0.5 0.5 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 75.9 75.9 dispersant Dispersant A weight% 0.5 0.5 0.5 Dispersant B weight% Dispersant C weight% catalyst weight% 0.1 0.1 0.1

[Table 24] Example 41 Example 42 Example 43 hardened matter Store modulus MPa 400 400 400 thermal conductivity W/m･K 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 80 80 80 thixotropic index - 2.5 2.5 2.5 Coating thickness of resin composition μm 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 Low temperature rapid hardening - △ △ △ Softness - 〇〇 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 6.00 6.00 6.00 determination - 〇 〇 〇

[Table 25] Example 44 Example 45 Example 46 Example 47 Resin composition Insulating filler Alumina A weight% 25.0 25.0 25.0 25.0 Alumina B weight% 60.0 60.0 60.0 60.0 Alumina C weight% Alumina D weight% Alumina 1 weight% Particle size (D90) μm 6.0 6.0 6.0 6.0 Particle size (D100) (maximum particle size) μm 8.0 8.0 8.0 8.0 thermosetting resin Epoxy Resin A weight% Epoxy Resin B weight% Epoxy Resin C weight% 6.3 3.4 3.3 6.3 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.6 4.8 1.6 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 41.5 67.6 80.0 heat hardener Butadiene compound polymer A weight% Butadiene compound polymer B weight% 6.0 4.7 9.0 6.0 Butadiene compound polymer C weight% Butadiene compound polymer D weight% Butadiene compound polymer E weight% Butadiene compound polymer F weight% Butadiene compound polymer G weight% Butadiene compound polymer H weight% Butadiene compound polymer I weight% Acid anhydride hardener A weight% 0.5 1.5 0.5 0.5 The content of the butadiene compound polymer in the thermal hardener relative to 100 parts by weight of the epoxy resin parts by weight 75.9 57.3 184.4 75.9 dispersant Dispersant A weight% 0.5 Dispersant B weight% 0.5 0.5 Dispersant C weight% 0.5 catalyst weight% 0.1 0.1 0.1 0.1

[Table 26] Example 44 Example 45 Example 46 Example 47 hardened matter Store modulus MPa 300 2000 500 500 thermal conductivity W/m･K 2.1 2.1 2.1 2.1 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 70 70 250 300 thixotropic index - 2.5 2.5 2.5 1.5 Coating thickness of resin composition μm 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 11.90 11.90 11.90 11.90 Low temperature rapid hardening - 〇 〇 〇〇 〇〇 Softness - 〇〇 △ 〇〇 〇〇 Heat dissipation - 〇〇 〇〇 〇〇 〇〇 Inhibition of warpage warp height μm 4.00 9.00 6.00 6.00 determination - 〇 △ 〇 〇

[Table 27] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Resin composition Insulating filler Alumina A weight% 25.0 25.0 15.0 Alumina B weight% 60.0 40.0 Alumina C weight% Alumina D weight% Alumina 1 weight% 60.0 Particle size (D90) μm 85.0 6.0 - - 6.0 Particle size (D100) (maximum particle size) μm 90.0 8.0 - - 8.0 thermosetting resin Epoxy Resin A weight% 30.0 Epoxy Resin B weight% 23.3 24.6 Epoxy Resin C weight% 6.8 17.4 Epoxy Resin D weight% Epoxy Resin E weight% Epoxy resin 1 weight% 1.7 7.0 6.7 52.0 1.6 Content of flexible epoxy resin in 100% by weight of epoxy resin weight% 80.0 0.0 88.8 25.0 94.0 heat hardener Acid anhydride hardener A weight% 30.6 Acid anhydride hardener B weight% 5.9 7.4 39.5 18.3 Acid anhydride hardener C weight% Phenol hardener A weight% Phenol hardener B weight% Phenol hardener C weight% dispersant Dispersant A weight% 0.5 Dispersant B weight% 0.5 0.5 catalyst weight% 0.1 0.1 0.5 0.1 0.1

[Table 28] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 hardened matter Store modulus MPa 350 2500 450 2500 1000 thermal conductivity W/m･K 2.1 2.1 0.3 0.3 0.6 Evaluation Viscosity at 25℃ and 10 rpm Pa･s 100 150 40 150 250 thixotropic index - 1.3 2.5 1.1 1.1 1.5 Coating thickness of resin composition μm 90.0 25.0 25.0 25.0 25.0 Thermal resistance of hardened material m･K･μm/W 42.86 11.90 83.33 83.33 41.67 Low temperature rapid hardening - × × × × × Softness - 〇〇 × 〇〇 × 〇 Heat dissipation - × 〇〇 × × × Inhibition of warpage warp height μm - 10.0 10.0 15.0 12.0 determination - - × × ×× ×

Furthermore, in Examples 1 to 16, 18 to 34, 36 to 47, and Comparative Examples 2 and 5, in the volume-based particle size distribution of the insulating filler, there is a region where the particle diameter is 0.1 μm or more and less than 1.0 μm. There is a peak in the region where the particle size is from 1.0 μm to 10 μm. Moreover, among the peaks (first peak) existing in the region where the particle diameter is 0.1 μm or more and less than 1.0 μm and the peak (second peak) existing in the region where the particle diameter is 1.0 μm or more and 10 μm or less, The peak height of the above-mentioned second peak is higher.

1:Semiconductor device 2:Substrate 3: Grain bonding material (hardened material of resin composition) 3A: Insulating filler 4: Semiconductor components

FIG. 1 is a cross-sectional view schematically showing a semiconductor device using a cured product of the resin composition according to the first embodiment of the present invention.

Claims (17)

A resin composition containing a thermosetting resin and an insulating filler, The maximum particle size of the above-mentioned insulating filler is 45 μm or less. When the cured product of the above resin composition is obtained by heating at 150°C for 2 hours, The thermal conductivity of the above-mentioned hardened material is 1.0 W/m･K or more, The storage modulus of the above-mentioned hardened material at 25°C is less than 2000 MPa. The resin composition of claim 1, wherein the thermal conductivity of the insulating filler is 10 W/m･K or more. For example, the resin composition of claim 1 or 2 has a viscosity of 150 Pa･s or less at 25°C and 10 rpm. For example, the resin composition of claim 1 or 2 has a ratio of the viscosity at 25°C and 1 rpm to the viscosity at 25°C and 10 rpm of 2.0 or more. The resin composition of claim 1 or 2, wherein the thermosetting resin includes epoxy resin. The resin composition of claim 5, wherein the epoxy resin includes a flexible epoxy resin. The resin composition of claim 6, wherein the content of the flexible epoxy resin in 100% by weight of the above-mentioned epoxy resin is not less than 30% by weight and not more than 90% by weight. The resin composition of claim 6, wherein the flexible epoxy resin includes polyalkylene glycol diglycidyl ether. The resin composition of claim 6, wherein the epoxy equivalent of the flexible epoxy resin is 300 g/eq or more and 1000 g/eq or less. The resin composition of claim 5, further comprising a thermohardener, The above-mentioned thermal hardener contains a polymer of butadiene compound, The polymer of the above-mentioned butadiene compound has more than two functional groups that can react with the epoxy group of the above-mentioned epoxy resin, The content of the polymer of the butadiene compound in the thermosetting agent is 25 parts by weight or more relative to 100 parts by weight of the epoxy resin. The resin composition of claim 1 or 2, wherein the insulating filler is made of alumina, synthetic magnesite, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide. The resin composition of claim 1 or 2, wherein the maximum particle size of the above-mentioned insulating filler is 25 μm or less. The resin composition of claim 1 or 2, wherein in the volume basis particle size distribution of the above-mentioned insulating filler, There are peaks in the region where the particle diameter is 0.1 μm or more and less than 1.0 μm, and in the region where the particle diameter is 1.0 μm or more and 10 μm or less. Such as the resin composition of claim 1 or 2, which in turn contains dispersants, The amine value of the above-mentioned dispersant is 40 KOHmg/g or more and 95 KOHmg/g or less. The acid value of the above-mentioned dispersant is 45 KOHmg/g or more and 95 KOHmg/g or less. Such as the resin composition of claim 1 or 2, which is a grain adhesive paste. A semiconductor device including a substrate, a die bonding material disposed on the surface of the substrate, and a semiconductor element disposed on the surface of the die bonding material, The above-mentioned die bonding material is a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor device including a substrate, a die bonding material disposed on the surface of the substrate, and a semiconductor element disposed on the surface of the die bonding material, The above-mentioned die bonding material is a hardened product of a resin composition containing a thermosetting resin and an insulating filler. The maximum particle size of the above-mentioned insulating filler is 45 μm or less. The thermal conductivity of the above-mentioned hardened material is 1.0 W/m･K or more, The storage modulus of the above-mentioned hardened material at 25°C is less than 2000 MPa.

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