WO2025187757A1 - Resin composition, heat-radiating member, and electronic apparatus - Google Patents

Abstract

This resin composition contains (A) at least one of a silicone resin and a silicone oil, (B) a compound represented by general formula (1) or (2), and (C) a thermally conductive filler.

Description

Resin composition, heat dissipation member, and electronic device

The present invention relates to a resin composition, a heat dissipation member formed from the composition, and an electronic component equipped with the heat dissipation member.

In recent years, the amount of heat generated by electronic devices has increased with the increasing integration of circuits, making heat management important, and the demand for heat dissipation materials has risen accordingly. Heat dissipation materials come in the form of sheets and greases. In particular, in recent years, heat dissipation materials made of silicone resins highly filled with thermally conductive fillers such as alumina have become increasingly popular for high heat dissipation.
When attempting to obtain a heat-dissipating material with high thermal conductivity by highly loading a thermally conductive filler into a silicone binder, the fluidity decreases as the amount of silicone decreases. To solve this problem, a method is known in which the thermally conductive filler is surface-treated with various surface treatment agents (alkoxysilanes, alkoxy-containing organopolysiloxanes, etc.).
For example, Patent Documents 1 to 3 describe inventions relating to thermally conductive silicone compositions containing a silicone resin, a thermally conductive filler, and an organopolysiloxane having a hydrolyzable group.
Furthermore, Patent Document 4 discloses a resin composition containing (A) a silicone resin or silicone oil, (B) a compound having a specific structure, and (C) a thermally conductive filler.

Japanese Patent Application Laid-Open No. 2000-256558 Patent No. 4745058 Patent No. 4514058 International Publication No. 2021/206064

Conventionally used thermally conductive silicone compositions have been unable to fully improve the decrease in fluidity that occurs when a thermally conductive filler is blended into the silicone, making it difficult to improve thermal conductivity to the desired level. Furthermore, the composition's physical properties tend to change at high temperatures, such as the viscosity increasing over time at high temperatures or the hardness increasing over time after curing, leaving room for improvement. Furthermore, with thermally conductive fillers that have low activity of surface functional groups, it has been difficult to achieve a sufficient viscosity-reducing effect using conventional surface treatment agents.

Furthermore, although the compound described in Patent Document 4 has a certain effect in dispersing fillers, there is a problem in that a large amount of impurities is generated during the synthesis, and the impurities cause unstable product quality.

The present invention aims to provide a resin composition that has good thermal conductivity, minimal changes in physical properties at high temperatures, and stable product quality.

As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by adjusting the ester bond to a specific position in the (B) compound, which is comprised of at least one of (A) a silicone resin and a silicone oil, (B) a compound represented by the following general formula (1) or (2), and (C) a thermally conductive filler, all of which are contained in a resin composition.
That is, the present invention provides the following [1] to [14].

[1] A resin composition containing (A) at least one of a silicone resin and a silicone oil, (B) at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and (C) a thermally conductive filler:


In the above formulas (1) and (2), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2, and n is an integer from 4 to 150.
[2] The resin composition according to [1] above, wherein the (C) thermally conductive filler is at least one selected from the group consisting of metal oxides, metal nitrides, carbides, carbon-based materials, and metal hydroxides.
[3] The resin composition according to [1] or [2] above, wherein the (C) thermally conductive filler is at least one selected from the group consisting of alumina, diamond, and aluminum nitride.
[4] The resin composition according to any one of [1] to [3] above, wherein the (C) thermally conductive filler contains two or more types of particles having different average particle sizes.
[5] The resin composition according to any one of the above [1] to [4], wherein the silicone resin (A) is an addition reaction curable silicone resin.
[6] Compound (B) represented by the following general formula (1) or (2):


In the above formulas (1) and (2), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2, and n is an integer from 4 to 150.
[7] The compound (B) according to the above item [6], which is used as a dispersant.
[8] A thermally conductive filler that has been surface-treated with the compound (B) described in [6] or [7] above.
[9] A resin composition comprising (A) at least one of a silicone resin and a silicone oil, and (B) the compound described in [6] or [7] above.
[10] A heat dissipation member formed from the resin composition according to any one of [1] to [5] or [9] above.
[11] An electronic device comprising an electronic component and the heat dissipation member according to [10] above, which is placed on the electronic component.
[12] A method for producing a compound (B), comprising subjecting a compound represented by the following general formula (3) to a hydrosilylation reaction with at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (5), to obtain at least one of a compound (B) represented by the following general formula (1) and a compound (B) represented by the following general formula (2):





In the above formulas (1) to (5), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2; and n is an integer from 4 to 150.
^R6 is an alkenyl group having 2 to 20 carbon atoms, which reacts with SiH in the above formula (3) to become ^R5 .
[13] A method for producing the compound (B) according to [12], comprising blending the compound represented by the general formula (3) and at least one of the compounds represented by the general formula (4) and the general formula (5) such that the reactive hydrogen group in the compound represented by the general formula (3) is in excess relative to the reactive alkenyl group in at least one of the compounds represented by the general formula (4) and the compound represented by the general formula (5).
[14] The method for producing the compound (B) according to [12] or [13], wherein the compound represented by the general formula (3) is removed after the completion of the hydrosilylation reaction.

The present invention makes it possible to provide a resin composition that has good thermal conductivity, exhibits minimal changes in physical properties at high temperatures, and provides stable product quality.

The resin composition of the present invention is a resin composition containing (A) at least one of a silicone resin and a silicone oil, (B) at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and (C) a thermally conductive filler.

In the above formulas (1) and (2), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2, and n is an integer from 4 to 150.

<(B) Compound>
In the present invention, at least one of the compounds (B) represented by the general formula (1) and the compounds represented by the general formula (2) (hereinafter sometimes simply referred to as the (B) compound) is used. The use of the (B) compound allows the surface treatment of the (C) thermally conductive filler, which will be described later. This improves the dispersibility of the (C) thermally conductive filler in the resin composition, thereby enabling the (C) thermally conductive filler to be highly loaded and increasing thermal conductivity. That is, the (B) compound functions as a dispersant for the thermally conductive filler. Therefore, the (B) compound can be used as a dispersant.

Furthermore, by using the compound (B) of the present invention, changes in the physical properties of the resin composition at high temperatures can be suppressed. This is presumably due to the ester structure of the compound (B). As shown in the chemical formula below, the thermal decomposition behavior of a compound having an ester bond and a carbon atom with a valence of two or more around it is generally known to result in a six-membered ring intermediate structure, which undergoes hydrogen abstraction at the γ-position of the carbonyl group, resulting in β-cleavage. Therefore, the chemical structure obtained by thermal decomposition takes on a carboxylic acid structure and exhibits high hydrogen bonding properties, which can interact with hydroxyl groups on the surface of the metal oxide and alkoxy groups not bonded to the filler to prevent volatilization.

In addition, the ester bond forms a hydrogen bond with a hydroxyl group on the surface of a metal oxide or a carbonyl group on the surface of a carbon-based material, thereby making it possible to obtain a higher dispersion effect than conventional surface treatment agents that contain only alkoxysilane.
Furthermore, since the compound (B) containing a small amount of impurities can be easily and stably produced, the compound (B) and resin composition having high quality can be stably produced. In addition, oil bleeding due to impurities can also be suppressed.

Among the compounds (B), the compounds represented by general formula (1) are as follows:

In the above formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different. The alkyl and alkenyl groups may be linear or branched. Among these, R ¹ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.
In the above formula (1), ^R2 is an alkyl group having 1 to 4 carbon atoms, and when there are multiple ^R2s (i.e., when a is 2), the multiple ^R2s may be the same or different. The alkyl group may be linear or branched. ^R2 is preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Furthermore, a is an integer from 0 to 2, and a is preferably 0 or 1, and more preferably 0.

In the above formula (1), ^R3 is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group. When there are multiple ^R3s (i.e., when a is 0 or 1), the multiple ^R3s may be the same or different. Furthermore, the alkyl group, alkoxyalkyl group, alkenyl group, and acyl group in ^R3 may be linear or branched. Among these, ^R3 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Specific examples of preferred alkyl groups include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and among these, a methyl group or an ethyl group is even more preferred.

In the above formula (1), R ⁴ is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 2 to 6 carbon atoms, and more preferably a butyl group.
In the above formula (1), ^R5 is an alkylene group having 2 to 20 carbon atoms, and multiple ^R5s may be the same or different. The alkylene group may be linear or branched. ^R5 is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, even more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably an alkylene group represented by —CH2 _—CH2 — _{CH2— or} —CH( _CH3 ) _—CH2— .

In the above formula (1), n represents the number of repeating units and is an integer between 4 and 150, preferably between 5 and 120, more preferably between 9 and 130, and even more preferably between 8 and 50. When n is within the above range, a relatively small amount can improve the dispersibility of the thermally conductive filler, and can also minimize changes in physical properties at high temperatures.

Among the compounds represented by the above formula (1), at least one of the compounds represented by the following formulas (1-1) and (1-2) is particularly preferred from the viewpoint of improving the dispersibility of the thermally conductive filler and obtaining a resin composition with little change in physical properties at high temperatures.


n is an integer from 4 to 150.

Among the compounds (B), the compounds represented by general formula (2) are as follows:

In the general formula (2), R ¹ , R ² , R ³ , R ⁵ , n, and a have the same meanings as those explained in the general formula (1) above.

Among the compounds represented by the formula (2), at least one of the compounds represented by the following formulas (2-1) and (2-2) is particularly preferred from the viewpoint of improving the dispersibility of the thermally conductive filler and obtaining a resin composition with little change in physical properties at high temperatures.


n is an integer from 4 to 150.

In the resin composition, as the compound (B), a compound represented by general formula (1) may be used, a compound represented by general formula (2) may be used, or both of them may be used.
The blending amount of the (B) compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the (C) thermally conductive filler. With such a blending amount, the surface treatment of the (C) thermally conductive filler with the (B) compound is appropriately carried out, and the dispersibility of the (C) thermally conductive filler is likely to be improved.

<(B) Method for producing compound>
The method for producing the compound (B) in the present invention is not particularly limited, but it is preferable to subject a compound represented by the following general formula (3) to a hydrosilylation reaction with at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (5) to obtain at least one of the compound (B) represented by the following general formula (1) and the compound (B) represented by the following general formula (2).
In this production method, the compound represented by general formula (4) may be used alone, or the compound represented by general formula (5) may be used alone, or these may be used in combination.
In this production method, the compound represented by general formula (3) may be blended with at least one of the compounds represented by general formula (4) and general formula (5) so that the reactive hydrogen groups are in excess relative to the reactive alkenyl groups. Here, the reactive alkenyl groups are reactive alkenyl groups in at least one of the compounds represented by general formula (4) and general formula (5), and the reactive hydrogen groups are reactive hydrogen groups in the compound represented by general formula (3). During the blending, the amount of reactive hydrogen groups is preferably 1.2 moles or more, more preferably 1.2 moles or more but 2.5 moles or less, per mole of reactive alkenyl groups.
In this production method, the compound represented by the general formula (3) may be removed after the hydrosilylation reaction is completed.
The production methods for obtaining the compound represented by the above formula (1) and the compound represented by the above formula (2) will be described in detail below.

For example, the compound represented by formula (1) can be obtained by a hydrosilylation reaction between a compound represented by formula (3) and a compound represented by formula (4): In this production method, it is preferable that the reactive hydrogen group in formula (3) is in excess in molar terms relative to the reactive alkenyl group in formula (4), and that after completion of the hydrosilylation reaction, the compound represented by formula (3) is removed by heating, by vacuum removal, or by heating and vacuum removal.

R ¹ to R ⁵ , n, and a in the above formulas (3) and (4) have the same meanings as those in formula (1). R ⁶ in formula (4) is an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 4 carbon atoms, and even more preferably a group represented by -C(CH ₃ )=CH _2. R ⁶ is a group that reacts with SiH in the above formula (3) to become R ⁵ .

The boiling point of the compound represented by formula (3) is preferably 250°C or lower, more preferably 180°C or lower, even more preferably 140°C or lower, and even more preferably 100°C or lower. When the boiling point of the compound represented by formula (3) is the above upper limit or lower, the unreacted compound represented by formula (3) can be easily removed by evaporation after completion of the reaction. Furthermore, the boiling point of the compound represented by formula (3) is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, so as to prevent evaporation during the hydrosilylation reaction.
Preferred specific examples of the compound represented by formula (3) include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, dimethoxymethylsilane, and diethoxymethylsilane, and among these, trimethoxysilane and triethoxysilane are more preferred.

The hydrosilylation reaction between the compound represented by formula (3) and the compound represented by formula (4) may be carried out using a hydrosilylation catalyst. The hydrosilylation catalyst is not particularly limited as long as it is a catalyst generally used in hydrosilylation reactions, and examples of the hydrosilylation catalyst that can be used include platinum alone and platinum supported on a support such as alumina, silica, or carbon black.
The hydrosilylation reaction between the compound represented by formula (3) and the compound represented by formula (4) may be carried out in the presence or absence of a solvent. Examples of solvents that can be used when carrying out the reaction in the presence of a solvent include toluene, hexane, and acetone. The reaction temperature is not particularly limited, but is preferably 25 to 150°C, more preferably 30 to 130°C. The reaction apparatus is not particularly limited, but since the compound represented by formula (3) is generally volatile and hydrolyzable, it is preferable to use an inert gas-sealed reactor. The compound represented by formula (3) and the compound represented by formula (4) are not particularly limited, but it is preferable that the reactive hydrogen group in the compound represented by formula (3) is in excess, as described above, relative to the reactive alkenyl group in the compound represented by formula (4), in terms of moles. The excess amount allows the compound represented by formula (4) to react completely, while leaving an excess of the compound represented by formula (3). However, since the compound represented by formula (3) is highly volatile and easy to remove, the excess compound represented by formula (3) can be removed by evaporation, thereby reducing the amount of impurities in the resin composition.
The compounding ratio of the compound represented by formula (3) to the compound represented by formula (4) is more preferably 1.2 moles or more, and even more preferably 1.2 moles or more to 2.5 moles or less, of the reactive hydrogen group in the compound represented by formula (3) relative to 1 mole of the reactive alkenyl group in the compound represented by formula (4).

The temperature at which the compound represented by formula (3) is removed by heating is preferably equal to or higher than the boiling point of the compound represented by formula (3), and specifically, is preferably 65 to 200° C., more preferably 70 to 180° C., and even more preferably 90 to 160° C. The time for removing by heating at the above temperature is not particularly limited, but is preferably 0.2 to 6 hours, more preferably 0.3 to 5 hours, and even more preferably 0.4 to 3 hours.
When the compound represented by formula (3) is removed by heating, it may be removed by heating under a reduced pressure environment as described above, or it may be removed by heating under a reduced pressure without heating. When the compound is removed by heating under a reduced pressure environment, the heating temperature may be within the above range or may be a temperature below the lower limit of the above temperature range.

The compound represented by formula (2) can be obtained by a hydrosilylation reaction between a compound represented by formula (3) and a compound represented by formula (5): In this production method, it is preferable that the reactive hydrogen group in formula (3) is in excess in molar terms relative to the reactive alkenyl group in formula (5), and that after completion of the hydrosilylation reaction, the compound represented by formula (3) is removed by heating, removal under reduced pressure, or removal under reduced pressure by heating.

R ¹ , R ² , R ³ , R ⁵ , n, and a in the above formulas (3) and (5) are defined the same as those in formula (1). R ⁶ in formula (5) is an alkenyl group having 2 to 10 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms, and more preferably a group represented by -C(CH ₃ )=CH _2. R ⁶ is also a group that reacts with SiH in the above formula (3) to become R ⁵ .

The reaction conditions, such as the catalyst, reaction temperature, reaction time, and solvent used in the hydrosilylation reaction of the compound represented by formula (3) with the compound represented by formula (5), are the same as those for the hydrosilylation reaction of the compound represented by formula (3) with the compound represented by formula (4).
The compounding ratio of the compound represented by formula (3) and the compound represented by formula (5) is not particularly limited, but it is preferable that the reactive hydrogen group in the compound represented by formula (3) is in excess in molar terms relative to the reactive alkenyl group in the compound represented by formula (5). With an excess amount, the compound represented by formula (5) is completely reacted while the compound represented by formula (3) becomes excess. However, since the compound represented by formula (3) is highly volatile and easy to remove, the excess compound represented by formula (3) can be removed by volatilization, and the amount of impurities in the resin composition can be reduced.
The compounding ratio of the compound represented by formula (3) and the compound represented by formula (5) is more preferably 1.2 moles or more, and even more preferably 1.2 moles or more and 2.5 moles or less, of the reactive hydrogen group in the compound represented by formula (3) relative to 1 mole of the reactive alkenyl group in the compound represented by formula (5).
The temperature, time, and heating method for the thermal removal after completion of the hydrosilylation reaction between the compound represented by formula (3) and the compound represented by formula (5) are the same as those described above.

In the production of compound (B) in the present invention, impurities other than compound (B) may be generated, or components other than compound (B) may remain as impurities. Examples of the generated or remaining impurities include compounds that did not react in the hydrosilylation reaction and were not removed by heating or reducing pressure, and by-products generated during the synthesis of compound (B).
In this production method, a step of further removing or reducing impurities may be carried out after the steps described above, but from the viewpoint of simplifying the process, the step of removing or reducing impurities may not be carried out. Furthermore, since the compound (B) can be produced by a method that can suppress the amount of impurities as described above, a highly pure compound (B) can be produced even without carrying out a step of further removing or reducing impurities.
Specifically, the amount of impurities in the (B) compound is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the (B) compound. When the amount of impurities is equal to or less than the above upper limit, the quality of the compound (B) is stable, and it is possible to stably provide resin compositions and heat-dissipating materials of good quality. Furthermore, oil bleeding due to impurities is suppressed. The amount of impurities is preferably as small as possible, and 0 parts by mass per 100 parts by mass of the produced (B) compound is particularly preferred. However, as long as the object of the present invention is not impaired, a certain amount of impurities may be generated, for example, 1 part by mass or more per 100 parts by mass of the produced (B) compound.

<(C) Thermally conductive filler>
In the present invention, a thermally conductive filler (C) is used. The thermally conductive filler (C) is surface-treated with the compound (B) described above, which improves dispersibility in the resin composition or in a cured product of the resin composition, thereby increasing thermal conductivity.
The thermally conductive filler (C) is not particularly limited, but is preferably at least one selected from the group consisting of metal oxides, metal nitrides, carbides, carbon-based materials, and metal hydroxides.
Examples of metal oxides include iron oxide, zinc oxide, silicon oxide (silica), alumina, magnesium oxide, titanium oxide, cerium oxide, and zirconium oxide.
Examples of metal nitrides include silicon nitride, aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, lithium nitride, and boron nitride.
Examples of carbides include silicon carbide, boron carbide, aluminum carbide, titanium carbide, and tungsten carbide.
Examples of carbon-based materials include diamond particles, carbon black, graphite, graphene, fullerene, carbon nanotubes, and carbon nanofibers.
Examples of metal hydroxides include aluminum hydroxide, calcium hydroxide, and magnesium hydroxide.
These thermally conductive fillers may be used alone or in combination of two or more kinds.

Among the above, the (C) thermally conductive filler is preferably at least one selected from the group consisting of alumina, diamond, and aluminum nitride, from the viewpoint that it can be surface-treated with the (B) compound described above, thereby improving dispersibility in the resin composition and facilitating improvement of thermal conductivity.

The average particle size of the primary particles of (C) the thermally conductive filler is not particularly limited, but is preferably 0.1 μm or more and 250 μm or less, and more preferably 0.2 μm or more and 100 μm or less.
The average particle size of the primary particles can be measured, for example, using a laser diffraction particle size distribution analyzer manufactured by Horiba, Ltd., and the particle size at which the cumulative volume is 50% (d50) may be taken as the average particle size of the primary particles.

(C) The thermally conductive filler preferably contains two or more types of particles having different average primary particle sizes. When two or more types of particles having different average primary particle sizes are used, the particles having a smaller average particle size are inserted between the particles having a larger average particle size, which makes it easier to increase the filling rate of the thermally conductive filler while properly dispersing the thermally conductive filler in at least one of the silicone resin and the silicone oil.
In addition, when two or more peaks appear in the particle size distribution of the thermally conductive filler, the resin composition can be determined to contain two or more types of particles with different average particle diameters of the primary particles.

(C) When the thermally conductive filler contains two or more types of particles with different average primary particle diameters, the specific particle diameter can be selected depending on the type of thermally conductive filler. For example, it is preferable to use a mixture of particles with an average primary particle diameter of 10 μm or more and 250 μm or less (large-particle-size thermally conductive filler) and a thermally conductive filler with an average primary particle diameter of 0.1 μm or more and less than 10 μm (small-particle-size thermally conductive filler). Furthermore, it is also preferable for the large-particle-size thermally conductive filler to contain two or more types of particles with different average primary particle diameters.

(C) The types of thermally conductive filler that can be used are those listed above. Furthermore, as mentioned above, the thermally conductive filler is preferably at least one selected from the group consisting of alumina, diamond, and aluminum nitride.

<Alumina>
When alumina is used as the (C) thermally conductive filler, it is preferable to include two or more types of particles with different average particle sizes of primary particles. When two or more types of particles with different average particle sizes are used, the particles with smaller average particle sizes enter between the particles with larger average particle sizes, making it easier to properly disperse the alumina in the silicone resin and increase the alumina filling rate.

When the alumina contains two or more types of particles with different average primary particle sizes, it is preferable that the alumina be a mixture of particles with an average primary particle size of 10 μm or more and 250 μm or less (hereinafter also referred to as "large particle size alumina") and particles with an average primary particle size of 0.1 μm or more and less than 10 μm (hereinafter also referred to as "small particle size alumina").

When the alumina contains both small particle size alumina and large particle size alumina, the mass ratio of large particle size alumina to small particle size alumina (large particle size/small particle size) is, for example, 0.1 or more and 50 or less, preferably 1 or more and 15 or less, and more preferably 5 or more and 15 or less. With such a mass ratio, the alumina is more likely to be filled into at least one of the silicone resin and silicone oil, which tends to improve thermal conductivity.

The large particle size alumina preferably has an average particle size of its primary particles of 12 μm or more and 100 μm or less, and more preferably 15 μm or more and 80 μm or less.
The small particle size alumina preferably has an average particle size of its primary particles of 0.2 μm or more and 5 μm or less, more preferably 0.2 μm or more and 3 μm or less.

<Diamond>
(C) When diamond is used as the thermally conductive filler, it is preferable to contain two or more kinds of particles with different average particle diameters of primary particles.When two or more kinds of particles with different average particle diameters are used, the particles with smaller average particle diameters get into the gaps between the particles with larger average particle diameters, and diamond is dispersed appropriately in at least one of silicone resin and silicone oil, and the filling rate of diamond is easily increased.

If the diamond contains two or more types of particles with different average primary particle diameters, it is preferable that the diamond be a mixture of particles with an average primary particle diameter of 10 μm or more and 250 μm or less (hereinafter also referred to as "large-grain diamonds") and particles with an average primary particle diameter of 0.1 μm or more and less than 10 μm (hereinafter also referred to as "small-grain diamonds").

When the diamonds contain both small-sized and large-sized diamonds, the mass ratio of large-sized diamonds to small-sized diamonds (large-sized diamonds/small-sized diamonds) is, for example, 0.5 or more and 20 or less, preferably 1 or more and 15 or less, and more preferably 2 or more and 8 or less. With such a mass ratio, the diamonds are easily filled into at least one of the silicone resin and silicone oil, which tends to improve thermal conductivity.

The large-grain diamond preferably has an average primary particle size of 15 μm or more and 150 μm or less, and more preferably 18 μm or more and 100 μm or less.
It is preferable that the large-grain diamond contains two or more types of primary particles with different average particle sizes, which makes it easier for the diamond to be filled with at least one of the silicone resin and the silicone oil, and tends to improve thermal conductivity.

The average particle size of the primary particles of the small-diameter diamond is preferably 0.5 μm or more and 8 μm or less, and more preferably 1 μm or more and 5 μm or less. Furthermore, the small-diameter diamond preferably contains two or more types of primary particles with different average particle sizes. This makes it easier for the diamond to be filled with at least one of the silicone resin and silicone oil, which tends to improve thermal conductivity.

<Aluminum nitride>
(C) When aluminum nitride is used as the thermally conductive filler, it is preferable to include two or more types of particles with different average primary particle diameters. When two or more types of particles with different average particle diameters are used, the particles with the smaller average particle diameter enter between the particles with the larger average particle diameter, making it easier to increase the filling rate of aluminum nitride while properly dispersing the aluminum nitride in the silicone resin.

When aluminum nitride contains two or more types of particles with different average primary particle sizes, it is preferable that the aluminum nitride be a mixture of particles with an average primary particle size of 10 μm or more and 250 μm or less (hereinafter also referred to as "large particle size aluminum nitride") and particles with an average primary particle size of 0.1 μm or more and less than 10 μm (hereinafter also referred to as "small particle size aluminum nitride").

When the aluminum nitride contains both small particle size aluminum nitride and large particle size aluminum nitride, the mass ratio of large particle size aluminum nitride to small particle size aluminum nitride (large particle size/small particle size) is, for example, 0.2 or more and 20 or less, preferably 0.3 or more and 10 or less, and more preferably 0.5 or more and 5 or less. With such a mass ratio, the aluminum nitride is easily filled into the silicone resin, which tends to improve thermal conductivity.

The large particle size aluminum nitride has an average particle size of its primary particles of preferably 10 μm or more and 100 μm or less, and more preferably 10 μm or more and 80 μm or less.
The large particle size aluminum nitride preferably contains two or more types of primary particles with different average particle sizes, which makes it easier for the aluminum nitride to be filled with at least one of the silicone resin and the silicone oil, and tends to improve thermal conductivity.

The small particle size aluminum nitride preferably has an average particle size of its primary particles of 1 μm or more and 8 μm or less, and more preferably 2 μm or more and 7 μm or less.
The small particle size aluminum nitride may contain two or more types of primary particles having different average particle sizes.

When the resin composition contains a thermally conductive filler (C), the amount of the thermally conductive filler (C) is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the resin composition. When the amount of the thermally conductive filler is equal to or greater than these lower limits, the thermal conductivity of the resin composition and its cured product is more easily improved.

Furthermore, the thermally conductive filler (C) of the present invention can be a thermally conductive filler that has been surface-treated using the compound (B) as described above.
The surface-treated thermally conductive filler can be obtained by mixing the compound (B) and the thermally conductive filler (C). In order to facilitate the surface treatment, it is preferable to use a wet treatment method, a dry treatment method, or the like when mixing.
In the wet treatment method, for example, the thermally conductive filler (C) is added to and mixed with a solution in which the compound (B) is dispersed or dissolved, and then the mixture is heated to bond or adhere the compound (B) to the surface of the thermally conductive filler.
The dry treatment method is a surface treatment method without using a solution, and specifically, it is a method in which the (C) thermally conductive filler and the above-mentioned (B) compound are mixed and stirred with a mixer or the like, and then heat-treated, thereby bonding or adhering the (B) compound to the surface of the thermally conductive filler. Note that the surface treatment carried out by mixing the (C) thermally conductive filler and the (B) compound can also be carried out in the presence of at least one of the (A) silicone resin and silicone oil described below.
The amount of the compound (B) used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of the thermally conductive filler (C).

<(A) At least one of silicone resin and silicone oil>
The resin composition of the present invention contains (A) at least one of a silicone resin and a silicone oil. The resin composition may contain the silicone resin alone, the silicone oil alone, or both.

(Silicone resin)
The type of silicone resin is not particularly limited, but condensation curing silicone resins and addition reaction curing silicone resins are preferred, and addition reaction curing silicone resins are more preferred.

Addition reaction curing silicone resins preferably consist of a silicone compound as the base agent and a curing agent that cures the base agent. The silicone compound used as the base agent is preferably an organopolysiloxane having an alkenyl group. Examples of alkenyl groups include those with 2 to 6 carbon atoms, such as vinyl groups, allyl groups, 1-butenyl groups, and 1-hexenyl groups, but vinyl groups are preferred from the perspective of ease of synthesis and cost. Furthermore, the silicone compound used as the base agent may have one or more alkenyl groups, but generally has two or more.

Specific examples of organopolysiloxanes having alkenyl groups include organopolysiloxanes having vinyl groups at both ends, such as polydimethylsiloxane having vinyl groups at both ends, polyphenylmethylsiloxane having vinyl groups at both ends, a copolymer of dimethylsiloxane having vinyl groups at both ends and diphenylsiloxane, a copolymer of dimethylsiloxane having vinyl groups at both ends and phenylmethylsiloxane, and a copolymer of dimethylsiloxane having vinyl groups at both ends and diethylsiloxane.
The silicone compound used as the base agent may have a viscosity at 25°C of, for example, 1000 mPa·s or less, preferably 50 mPa·s or more, more preferably 80 mPa·s or more and 800 mPa·s or less, and even more preferably 100 mPa·s or more and 500 mPa·s or less.

The curing agent used in the addition reaction curing silicone resin is not particularly limited as long as it can cure the silicone compound that is the main component described above. However, organohydrogenpolysiloxane, which is an organopolysiloxane having two or more hydrosilyl groups (SiH), is preferred.
Examples of organohydrogenpolysiloxanes include methylhydrosiloxane-dimethylsiloxane copolymers, polymethylhydrosiloxanes, polyethylhydrosiloxanes, methylhydrosiloxane-phenylmethylsiloxane copolymers, etc. These may or may not contain hydrosilyl groups at the terminals.
The viscosity of the curing agent at 25°C is preferably 1000 mPa·s or less, preferably 50 mPa·s or more, more preferably 100 mPa·s or more and 900 mPa·s or less, and even more preferably 100 mPa·s or more and 600 mPa·s or less.
By setting the viscosity ranges of the base resin and the curing agent as described above, the viscosity of the resin composition can be reduced, improving workability, and the thermally conductive filler can be easily dispersed and incorporated into the resin composition in large amounts.

When using silicone resin, a curing catalyst is usually added. Examples of curing catalysts include platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts, with platinum-based catalysts being preferred. The curing catalyst is used to cure the silicone compound, which is the raw material for silicone resin, and the curing agent. The amount of curing catalyst added is usually 0.1 to 200 ppm, preferably 0.5 to 100 ppm, based on the total mass of the silicone compound and curing agent.

The silicone resin may be either a one-component curing type or a two-component curing type. In the two-component curing type, the resin composition may be prepared by mixing the first component containing the base resin and the second component containing the curing agent. In the case of the two-component curing type, the (C) thermally conductive filler and the (B) compound may be blended in either the first component or the second component, or in both components.
When using silicone oil, using a compound represented by general formula (1) and a compound represented by general formula (2) together as compound (B) is more effective than using each compound alone, and is desirable from the viewpoint of being able to suppress voids that occur when the composition is left standing at high temperatures after application, and is effective for one-component non-curing heat-dissipating compounds.

(silicone oil)
The silicone oil is preferably a non-reactive silicone oil that does not have reactive groups such as alkoxy groups or silanol groups in the molecule, but it may also be a reactive silicone oil having reactive groups, a reaction product of a reactive silicone, or a mixture of various silicone oils, as long as it is liquid.
Examples of silicone oil include straight silicone oil and modified silicone oil, with straight silicone oil being preferred.
Examples of straight silicone oils include polyorganosiloxanes such as dimethyl silicone oil and phenylmethyl silicone oil.
Examples of modified silicone oils include polyether-modified silicone oils, aralkyl-modified silicone oils, fluoroalkyl-modified silicone oils, long-chain alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, higher fatty acid amide-modified silicone oils, and phenyl-modified silicone oils.

The viscosity of the silicone oil at 25°C is preferably 20 mPa·s or more and 500 mPa·s or less, more preferably 50 mPa·s or more and 300 mPa·s or less, and even more preferably 80 mPa·s or more and 150 mPa·s or less.

The content of at least one of (A) silicone resin and (C) silicone oil is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass per 100 parts by mass of (C) thermally conductive filler.

As described above, the resin composition of the present invention is a resin composition containing at least one of (A) a silicone resin and a silicone oil, a (B) compound, and a (C) thermally conductive filler. The order of blending these components is not particularly limited, but the resin composition can be prepared by mixing all of these components. In this case, the (B) compound adheres to or reacts with the surface of the (C) thermally conductive filler in the composition, thereby increasing the dispersibility of the (C) thermally conductive filler in at least one of the (A) silicone resin and the silicone oil.
Alternatively, the resin composition may be prepared by first mixing the (B) compound with the (C) thermally conductive filler, allowing the (B) compound to adhere to or react with the surface of the (C) thermally conductive filler, and then further mixing in at least one of the (A) silicone resin and the (A) silicone oil.
As described above, it is also preferable to prepare the liquid 1 by mixing the liquid 2. When preparing the liquid 1 and the liquid 2, it is also preferable to prepare them by mixing the various components in the same manner.

In addition to the resin composition containing all of the above-mentioned (A) to (C), the present invention can also provide a resin composition containing (A) at least one of a silicone resin and a silicone oil, and (B) a compound. A resin composition containing (A) at least one of a silicone resin and a silicone oil, and (B) a compound can be used as a filling composition for (C) a thermally conductive filler, and can be used by appropriately blending (C) a thermally conductive filler.

The resin composition of the present invention may contain additives such as antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents, as needed.

The resin composition of the present invention can be used as a raw material to produce a heat dissipation member formed from the resin composition. For example, the resin composition can be formed into a predetermined shape and then cured by appropriate heating or the like to produce a heat dissipation member molded into the predetermined shape.
The heat dissipation member can be used, for example, inside an electronic device, and in that case, the electronic device can include an electronic component and the heat dissipation member disposed on the electronic component. Specifically, the heat dissipation member can be disposed between an electronic component such as a semiconductor element and a heat sink to effectively dissipate heat generated from the electronic component.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples in any way.

The samples prepared in each example and comparative example were evaluated as follows. When silicone resin was used as component (A), the magnitude of changes in physical properties at high temperatures was evaluated using the "rate of hardness change," and when silicone oil was used as component (A), the magnitude of changes in physical properties at high temperatures was evaluated using the "rate of viscosity change" or "rate of change in piercing load."

[Hardness change rate]
The rate of change in hardness was calculated from the initial hardness of the cured product of the resin composition prepared in Examples 1 to 9 and Comparative Examples 1 to 13 and the hardness after heat treatment at 150°C for 200 hours using the following formula.
Hardness change rate (%) = [(hardness after heat treatment - initial hardness) / initial hardness] x 100
The hardness was measured as Type E hardness using an automatic hardness measuring device, "GX-02E" manufactured by Teclock Corporation.

[Viscosity change rate]
The viscosity change rate was calculated from the initial viscosity of the resin compositions prepared in Examples 20 to 22 and Comparative Examples 18 and 29 and the viscosity after heat treatment at 150°C for 200 hours using the following formula.
Viscosity change rate (%) = [(viscosity after heat treatment - viscosity in initial state) / viscosity in initial state] x 100
The viscosity was measured at 23°C using a Brookfield B-type viscometer.
The measurement device used was "HB DVE" manufactured by Eiko Seiki Co., Ltd.

[Penetration load change rate]
The piercing load change rate was calculated using the following formula from the piercing load in the initial state of the resin compositions prepared in Examples 10 to 19, 23 to 26 and Comparative Examples 14 to 17, 19 to 28, and 30 to 33 and the piercing load after heat treatment at 150 ° C. for 200 hours.
Penetration load change rate (%) = [(Penetration load after heat treatment - Initial piercing load) / Initial piercing load] x 100
The penetration load was measured by piercing a needle into the sample and measuring the load when the needle reached a depth of 6 mm from the surface.
The piercing load was measured using a piercing load measuring machine, a digital force gauge "ZTS-5N" manufactured by IMADA, under the conditions of a needle diameter of 1 mm, a piercing speed of 10 mm/min, and a measurement temperature of 23°C.

[Thermal conductivity]
The thermal conductivity was measured at 23° C. in accordance with ASTM D5470 using a measuring device, "T3Ster DynTIM Tester" manufactured by Mentor, a Siemens Business.
[Furnishing]
The measurement was carried out in accordance with JIS K-2220 using a quarter cone.
[Void ratio]
0.5 g of the paste-like resin composition was applied to an alumina substrate, and pressed with a glass plate to a thickness of 1 mm, and then stored in this fixed state for 24 hours at 150° C. The void ratio was calculated by dividing the area of voids observed after storage by the total area of the paste-like resin composition.
<Judgment criteria>
The void ratio was judged according to the following criteria.
A: Void ratio is 10% or less. B: Void ratio is more than 10% and less than 15%. C: Void ratio is more than 15% and less than 20%.

[Oil bleed]
0.5 g of the paste-like resin composition was applied to a ground glass, and the distance of oil seepage after 24 hours at 150° C. was measured.
<Judgment criteria>
The oil bleeding was evaluated according to the following criteria.
A: Bleed distance 2mm or less B: Bleed distance over 2mm and 3mm or less C: Bleed distance over 3mm

The components used in each of the examples and comparative examples are as follows.
<Component (A): Silicone Resin>
Addition reaction type silicone resin. Main component: vinyl-terminated organopolysiloxane (viscosity at 25°C: 300 mPa·s)
Curing agent: Organohydrogenpolysiloxane (viscosity at 25°C: 400 mPa·s)
<Component (A): Silicone Oil>
Polyorganosiloxane (viscosity at 25°C: 110 mPa·s)

<(B) Compound>
As compounds represented by general formula (1), "treatment agent 1,""treatment agent 2,""treatment agent 3,""treatment agent 5," and "treatment agent 6" were used, and as a compound represented by general formula (2), "treatment agent 4" was produced as follows.

[Production of Treatment Agent 1]
Triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), Gelest's "MCR-M17," and a hydrosilylation catalyst were charged into a reactor, which was then filled with nitrogen and heated at 70°C for 2 hours while the reactor was sealed. The reactor lid was then opened, and the reactor was heated at 150°C for 0.5 hours with the lid still open, thereby producing Treatment Agent 1. During the charging process, triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "MCR-M17" were blended such that 2 moles of reactive hydrogen groups in triethoxysilane were present for every 1 mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight.
The reaction scheme is as follows, in which n is 55-75.

[Preparation of Treatment Agent 2]
Treatment agent 2 was produced in the same manner as treatment agent 1, except that "MCR-M17" was replaced with "MCR-M22" manufactured by Gelest, which has a higher molecular weight. The reaction scheme is the same as that for treatment agent 1, except that n is 120 to 140, and therefore will not be described here.

[Preparation of Treatment Agent 3]
Trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), Gelest's "MCR-M17," and hydrosilylation agent were charged into a reactor, which was then filled with nitrogen and heated at 50°C for 3 hours while the reactor was sealed. The reactor lid was then opened, and the reactor was heated at 100°C for 0.5 hours with the lid still open, thereby producing Treatment Agent 3. During the charging process, trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "MCR-M17" were blended so that 2 moles of reactive hydrogen groups in trimethoxysilane were present for every 1 mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight.
The reaction scheme is as follows, in which n is 55-75.

[Preparation of Treatment Agent 4]
Triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), Gelest's "DMS-R18," and hydrosilylation agent were charged into a reactor, which was then filled with nitrogen and heated at 70°C for 2 hours while the reactor was sealed. The reactor lid was then opened, and the reactor was heated at 150°C for 0.5 hours with the lid open, thereby producing Treatment Agent 4. During the charging process, triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "DMS-R18" were blended so that the reactive hydrogen groups of triethoxysilane were 2 moles per mole of reactive alkenyl groups of "DMS-R18" calculated from the molecular weight.
The reaction formula is as follows, in which n is 50 to 70.

The above treating agents 1, 2 and 4 were identified by ¹ H-NMR.
¹ H-NMR (CDCl ₃ ), apparatus name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4 T, temperature 25° C., sample concentration 10 wt %, number of accumulations 8:
δ 4.02ppm (m, 2H, -COO-CH ₂ -),
3.82 ppm (q, J = 6.8 Hz, 6H, -Si-O-CH ₂ -),
2.65ppm (m, 1H, -OCO-CH-),
1.65 ppm (m, 2H, -COOCH ₂ -CH ₂ -),
2.32 ppm (m, 4H, -SiCH ₂ -C ₂ H ₄ -),
1.23 ppm (d, J = 6.8 Hz, 3H, -OCOCH-CH ₃ ),
1.22 ppm (t, J = 6.8 Hz, 9H, -SiOCH ₂ -CH ₃ ),
1.12ppm (dd, J=5.6, 14.2Hz, 1H, OCOCH(CH ₃ )-CH(H)-),
0.88 ppm (t, J=7.2Hz, 3H-SiC ₂ H ₆ -CH ₃ ),
0.77ppm (dd, J=7.2, 14.2Hz, 1HOCOCH( _CH3 )CH-H-),
0.54 ppm (m, 4H, -Si-CH ₂ -C ₃ H ₇ /-COOC ₂ H ₄ -CH ₂ -)
0.08ppm (m, 436H, -Si-(CH ₃ ) ₂ )

[Production of Treatment Agent 5]
Treatment agent 5 was produced in the same manner as treatment agent 1, except that the amount of triethoxysilane was adjusted so that there were 1.5 moles of reactive hydrogen groups in triethoxysilane per mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight. The reaction formula is the same as for treatment agent 1, and therefore is omitted here.

[Production of Treatment Agent 6]
Treatment agent 6 was produced in the same manner as treatment agent 1, except that the amount of triethoxysilane was adjusted so that there were 1.2 moles of reactive hydrogen groups in triethoxysilane per mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight. The reaction formula is the same as for treatment agent 1, so it is omitted here.

The compounds used in the comparative examples, "Treatment Agent 7," "Treatment Agent 8," and "Treatment Agent 11," were prepared and used as follows:

[Production of Treatment Agent 7]
"KBM-503" manufactured by Shin-Etsu Silicones Co., Ltd. and "MCR-H11" manufactured by Gless Co., Ltd. were reacted in the presence of a hydrosilylation catalyst to obtain treatment agent 7. The reaction temperature was 150°C, the reaction time was 0.5 hours, and the amount of "KBM-503" added was 1 mole per mole of "MCR-H11."
The reaction scheme is as follows, in which n is 5 or 6.

[Production of Treatment Agent 8]
Treatment agent 8 was produced in the same manner as treatment agent 7, except that Gelest's "MCR-H21" was used instead of MCR-H11. The reaction scheme is the same as that for treatment agent 7, and therefore will not be described here.

[Production of Treatment Agent 11]
Treating agent 11 was produced in the same manner as treating agent 7, except that "DMS-H21" manufactured by Gelest was used instead of "MCR-H11" manufactured by Gelest, so as to have the following structure. In the following structure, n is 60 to 80.

The treating agents 7, 8 and 11 were identified by ²⁹ Si-NMR and ¹ H-NMR.
¹ H-NMR (CDCl ₃ ), apparatus name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4 T, temperature 25° C., sample concentration 10 wt %, number of accumulations 8:
δ 4.70-4.66ppm (m, 1H, HSi),
3.56 ppm (s, 9H, Si(OCH ₃ ) ₃ ),
2.58 to 2.42 ppm (m, 1H, OOCCH (CH ₃ )),
1.09-0.56ppm (m, 4H, Si(CH ₂ ) ₂ Si),
0.17-0.02 ppm (m, 18H, Si(CH ₃ ) ₂ O).

Furthermore, the compounds used in the comparative examples were "Treatment Agent 9," "Treatment Agent 10," and "Decyltrimethoxysilane," which have the structures shown below.

[Treatment agent 9]

n is 8 to 10.
[Treatment agent 10]
In the structure of the above-mentioned treating agent 9, n is a compound of 60 to 80.

[Decyltrimethoxysilane]

<Component (C): Thermally Conductive Filler>
<Alumina>
"Alumina 1" average particle size 40 μm
"Alumina 2" average particle size 13 μm
"Alumina 3" average particle size 0.5 μm
"Alumina 4" average particle size 3 μm
Diamond
"Diamond 1" average particle size 3 μm
"Diamond 2" average particle size 7 μm
"Diamond 3" average particle size 10 μm
"Diamond 4" average particle size 20 μm
"Diamond 5" average particle size 40 μm
"Diamond 6" average particle size 70 μm
"Diamond 7" average particle size 50 μm
<Aluminum nitride>
"Aluminum nitride 1" Average particle size 50 μm
"Aluminum nitride 2" average particle size 30 μm
"Aluminum nitride 3" Average particle size 10 μm
"Aluminum nitride 4" average particle size 5 μm
The average particle diameters of the above-mentioned Alumina 1 to 4, Diamond 1 to 7, and Aluminum Nitride 1 to 4 are the average particle diameters of primary particles.

[Example 1]
To 5.2 parts by mass of organopolysiloxane (viscosity at 25°C: 300 mPa s) vinyl-terminated at both ends, which constitutes the main component of the addition reaction type silicone resin, compound (B) as a dispersant and thermally conductive filler (C) were added in the blending parts shown in Table 1, and 1.5 parts by mass of a reaction retarder and a catalytic amount of a platinum catalyst were further added to prepare a one-part resin composition.
Furthermore, a second liquid of the resin composition was prepared by adding the compound (B) as a dispersant and the thermally conductive filler (C) in the blending parts shown in Table 1 to 5.2 parts by mass of organohydrogenpolysiloxane (viscosity at 25°C: 400 mPa s) constituting the curing agent for the addition reaction type silicone resin.
The first and second components were mixed at a mass ratio (first component/second component) of 1:1, then poured into a mold and heated at 70°C for 1 hour to promote the curing reaction. The resulting cured resin composition was stored at 23°C for 12 hours, and the initial hardness of the cured resin composition was evaluated at the point when no change in hardness was observed.

[Examples 2 to 9, Comparative Examples 1 to 13]
Cured resin compositions were obtained in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 1.

[Examples 10 to 26, Comparative Examples 14 to 33]
A paste-like resin composition was prepared by mixing silicone oil, a thermally conductive filler, and a dispersant according to the formulation shown in Table 2. The resin composition was heated at 150°C for 1 hour, and then allowed to stand at 23°C for 12 hours, after which the initial state was evaluated.
[Examples 27 to 29, Comparative Examples 34 to 38]
Paste-like resin compositions were prepared by mixing silicone oil, a thermally conductive filler, and a dispersant according to the formulation shown in Table 3. The void ratio of the prepared resin compositions was calculated at room temperature and after 24 hours at 150°C.

[Examples 30 to 32]
Treatment agent 1 was prepared in three batches by changing the material lot and scale so that each batch contained the parts by mass shown in Table 4. The purity and impurity concentration were quantified by NMR ( ¹ H-NMR (CDCl ₃ ), apparatus name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4 T, temperature 25°C, sample concentration 10 wt %, accumulation number 8), and the remaining amount of triethoxysilane, remaining amount of MCR-M17, remaining amount of non-reactive impurities, remaining amount of MCR-H11, and remaining amount of KBM503 were determined.

[Comparative Examples 39 to 44]
Six batches of treatment agent 7 were prepared by changing the material lot and scale so that each batch contained the parts by mass shown in Table 4. The purity and impurity concentration were quantified by NMR ( ¹ H-NMR (CDCl ₃ ), apparatus name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4 T, temperature 25°C, sample concentration 10 wt %, accumulation number 8), and the remaining amounts of triethoxysilane, MCR-M17, non-reactive impurities, MCR-H11, and KBM503 were determined.

[Examples 33 to 37, Comparative Examples 45 to 50]
According to the method of Example 1, the effect of each treatment agent on hardness was measured using the formulations shown in Table 5.

[Examples 38 to 42, Comparative Examples 51 to 53]
A paste-like resin composition was prepared by mixing silicone oil, a thermally conductive filler, and a dispersant according to the formulation shown in Table 6. The resin composition was heated at 150°C for 1 hour and allowed to stand at 23°C for 12 hours. Approximately 0.5 g of the composition was then applied to a frosted glass, and the amount of oil seeping out after 24 hours at 150°C was evaluated.

*The treatment agents in Table 5 are as follows:
Treatment agent 1 (Lot #1) → Treatment agent 1 prepared in Example 30
Treatment agent 1 (Lot #2) -> Treatment agent 1 prepared in Example 31
Treatment agent 1 (Lot #3) -> Treatment agent 1 prepared in Example 32
Treatment agent 7 (Lot #1) -> Treatment agent 7 prepared in Comparative Example 39
Treatment agent 7 (Lot #2) -> Treatment agent 7 prepared in Comparative Example 40
Treatment agent 7 (Lot #3) -> Treatment agent 7 prepared in Comparative Example 41

When comparing resin compositions containing the same type and amount of thermally conductive filler between Examples and Comparative Examples, it was confirmed that the Examples had a smaller rate of change in each physical property than the Comparative Examples, and that the impact of lot variation on properties was smaller, resulting in stable product quality. In particular, when the (B) compound to be contained in silicone oil is used, a resin composition with superior performance can be obtained by using a compound having trialkoxy groups at both ends of the silicone chain, as in the structure of formula (2). This shows that the resin composition of the present invention using a (B) compound having a specific structure has good thermal conductivity and a small rate of change in physical properties at high temperatures.
On the other hand, as is clear from Comparative Examples 39 to 53, it was found that resin compositions using compounds without a specific structure had unstable impurity amounts even when the same type of compound was used, and the performance exhibited by the resin composition varied greatly depending on the compound used, resulting in unstable quality.

Claims (14)

(A) at least one of a silicone resin and a silicone oil;
(B) at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2),
(C) a thermally conductive filler.


In the above formulas (1) and (2), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2, and n is an integer from 4 to 150. The resin composition according to claim 1, wherein the (C) thermally conductive filler is at least one selected from the group consisting of metal oxides, metal nitrides, carbides, carbon-based materials, and metal hydroxides. The resin composition according to claim 1 or 2, wherein the (C) thermally conductive filler is at least one selected from the group consisting of alumina, diamond, and aluminum nitride. The resin composition according to claim 1 or 2, wherein the thermally conductive filler (C) contains two or more types of particles having different average particle sizes. The resin composition according to claim 1 or 2, wherein the (A) silicone resin is an addition reaction curable silicone resin. A compound (B) represented by the following general formula (1) or (2):


In the above formulas (1) and (2), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2, and n is an integer from 4 to 150. The compound (B) described in claim 6, which is used as a dispersant. A thermally conductive filler surface-treated with the compound (B) described in claim 6 or 7. A resin composition comprising (A) at least one of a silicone resin and a silicone oil, and (B) the compound described in claim 6 or 7. A heat dissipation component formed from the resin composition described in claim 1 or 2. An electronic device comprising an electronic component and the heat dissipation member described in claim 10 disposed on the electronic component. A method for producing compound (B), comprising subjecting a compound represented by the following general formula (3) to a hydrosilylation reaction with at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (5), to obtain at least one of compound (B) represented by the following general formula (1) and compound (B) represented by the following general formula (2):





In the above formulas (1) to (5), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and multiple R ^1s may be the same or different from each other; R ² is an alkyl group having 1 to 4 carbon atoms, and when there is multiple R ^2s , the multiple R ^2s may be the same or different from each other; R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an acyl group, and when there is multiple R ^3s , the multiple R ^3s may be the same or different from each other; R ⁴ is an alkyl group having 1 to 8 carbon atoms; R ⁵ is an alkylene group having 2 to 20 carbon atoms, and the multiple R ^5s may be the same or different from each other; a is an integer from 0 to 2; and n is an integer from 4 to 150.
^R6 is an alkenyl group having 2 to 20 carbon atoms, which reacts with SiH in the above formula (3) to become ^R5 . The method for producing compound (B) according to claim 12, comprising blending the compound represented by general formula (3) with at least one of the compounds represented by general formula (4) and general formula (5) so that the reactive hydrogen groups in the compound represented by general formula (3) are in excess relative to the reactive alkenyl groups in at least one of the compounds represented by general formula (4) and general formula (5). The method for producing compound (B) according to claim 12 or 13, wherein the compound represented by general formula (3) is removed after completion of the hydrosilylation reaction.