Resin composition, heat-radiating member, and electronic apparatus

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

[0001] 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.

[0002] In recent years, the increasing heat generated by electronic devices due to the increasing integration of circuits has made heat management important, leading to a growing demand for heat-dissipating materials. Heat-dissipating materials are available in the form of sheets and greases. In particular, in recent years, heat-dissipating materials made of silicone resins highly filled with thermally conductive fillers such as alumina have become increasingly popular for achieving high heat dissipation. When attempting to highly fill the silicone binder with thermally conductive fillers to obtain heat-dissipating materials with high thermal conductivity, fluidity decreases as the silicone content decreases. To address this issue, methods of surface treating thermally conductive fillers using various surface treatment agents (e.g., alkoxysilanes, alkoxy-containing organopolysiloxanes, etc.) have been known. For example, Patent Documents 1 to 3 describe inventions related to thermally conductive silicone compositions containing a silicone resin, a thermally conductive filler, and an organopolysiloxane having a hydrolyzable group. Patent Document 4 also 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.

[0003] Japanese Patent Publication No. 2000-256558 Japanese Patent No. 4745058 Japanese Patent No. 4514058 International Publication No. 2021 / 206064

[0004] Conventional thermally conductive silicone compositions have not been able to sufficiently improve the decrease in fluidity that occurs when a thermally conductive filler is blended into the silicone, making it difficult to improve the 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, for thermally conductive fillers with low surface functional group activity, it has been difficult to achieve a sufficient viscosity reduction effect using conventional surface treatment agents.

[0005] Furthermore, although the compound described in Patent Document 4 has a certain effect of dispersing fillers, there is a problem in that a large amount of impurities are generated during the synthesis thereof, and the quality of the product is unstable due to the impurities.

[0006] Therefore, an object of the present invention is to provide a resin composition that has good thermal conductivity, undergoes little change in physical properties at high temperatures, and provides stable product quality.

[0007] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by adjusting the ester bond at 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] .

[0008] [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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５may be the same or different, a is an integer of 0 to 2, and n is an integer of 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 [1] to [4] above, wherein the (A) silicone resin is an addition reaction curable silicone resin. [6] A (B) compound 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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５may be the same or different, a is an integer of 0 to 2, and n is an integer of 4 to 150. [7] The (B) compound according to the above item [6], used as a dispersant. [8] A thermally conductive filler surface-treated with the (B) compound according to the above item [6] or [7]. [9] A resin composition containing at least one of (A) a silicone resin and a silicone oil, and the (B) compound according to the above item [6] or [7].

[10] A heat dissipation member formed from the resin composition according to any one of items [1] to [5] or [9].

[11] An electronic device comprising an electronic component and the heat dissipation member according to the above item

[10] , disposed on the electronic component.

[12] A method for producing a (B) compound, 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 (B) compound represented by the following general formula (1) and a (B) compound 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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different, a is an integer of 0 to 2, n is an integer of 4 to 150, R６ is an alkenyl group having 2 to 20 carbon atoms, which reacts with SiH in the above formula (3) to form R ５

[13] A method for producing compound (B) according to

[12] , comprising blending a compound represented by general formula (3) and at least one of a compound represented by general formula (4) and a compound represented by general formula (5) such 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 a compound represented by general formula (4) and a compound represented by general formula (5).

[14] A method for producing compound (B) according to

[12] or

[13] , comprising removing the compound represented by general formula (3) after completion of the hydrosilylation reaction.

[0009] According to the present invention, it is possible to provide a resin composition which has good thermal conductivity, undergoes little change in physical properties at high temperatures, and provides stable product quality.

[0010] 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:

[0011] 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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different, a is an integer of 0 to 2, and n is an integer of 4 to 150.

[0012] <(B) Compound> In the present invention, at least one of the compounds (B) represented by the above general formula (1) and the compounds represented by the above general formula (2) (hereinafter sometimes simply referred to as (B) compound) is used. By using the (B) compound, the surface treatment of the thermally conductive filler (C) described below is performed. This improves the dispersibility of the thermally conductive filler (C) in the resin composition, resulting in a high loading of the thermally conductive filler (C), and increased thermal conductivity. In other words, the (B) compound functions as a dispersant for the thermally conductive filler. Therefore, the (B) compound can be used as a dispersant.

[0013] 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 achieving a higher dispersion effect than conventional surface treatment agents containing only alkoxysilane. Furthermore, since compound (B) with a low impurity content can be easily and stably produced, compound (B) and resin compositions with high quality can be stably produced. Oil bleeding due to impurities can also be suppressed.

[0014] Among the compounds (B), the compounds represented by general formula (1) are as follows:

[0015] 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 a plurality of R １ may be the same or different. The alkyl group and alkenyl group may be linear or branched. 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. ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are a plurality of R ２ may be the same or different. The alkyl group may be a straight chain or a branched chain. ２ is preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Furthermore, a is an integer of 0 to 2, and a is preferably 0 or 1, and more preferably 0.

[0016] In the above formula (1), 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 R ３ When there are a plurality of R (i.e., when a is 0 or 1), the plurality of R ３ may be the same or different. ３ The alkyl group, alkoxyalkyl group, alkenyl group, and acyl group in R may be linear or branched. ３ 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.

[0017] 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. ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different. The alkylene group may be a straight chain or a branched chain. ５ is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms; ２ -CH ２ -CH ２ - or -CH(CH ３ )-CH ２ An alkylene group represented by - is more preferred.

[0018] In the above formula (1), n ​​represents the number of repetitions and is an integer of 4 to 150, preferably an integer of 5 to 120, more preferably an integer of 9 to 130, and even more preferably an integer of 8 to 50. When n is within the above range, the dispersibility of the thermally conductive filler can be improved with a relatively small amount, and further, changes in physical properties at high temperatures can be reduced.

[0019] 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.

[0020] Among the compounds (B), the compounds represented by general formula (2) are as follows: In general formula (2), R １ , R ２ , R ３ , R ５ , n, and a have the same meanings as those explained in the above general formula (1).

[0021] 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.

[0022] In the resin composition, the (B) compound may be a compound represented by general formula (1), a compound represented by general formula (2), or both. The 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 an 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.

[0023] <Method for Producing Compound (B)> The method for producing compound (B) in the present invention is not particularly limited, but may be a hydrosilylation reaction between a compound represented by general formula (3) below and at least one of a compound represented by general formula (4) below and a compound represented by general formula (5) below, to obtain at least one of compound (B) represented by general formula (1) below and compound (B) represented by general formula (2) below. 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 compounds represented by general formula (4) and general formula (5) such that the reactive hydrogen group is in excess relative to the reactive alkenyl group. Here, the reactive alkenyl group is a reactive alkenyl group in at least one of compounds represented by general formula (4) and general formula (5), and the reactive hydrogen group is a reactive hydrogen group in the compound represented by general formula (3). In the above blending, the amount of reactive hydrogen groups is preferably 1.2 moles or more, more preferably 1.2 moles or more and 2.5 moles or less, per mole of reactive alkenyl groups. In this production method, the compound represented by general formula (3) may be removed after completion of the hydrosilylation reaction. Hereinafter, the production methods for obtaining the compound represented by formula (1) and the compound represented by formula (2) will be described in detail.

[0024] 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 in the above formulas (3) and (4) １ ~R ５, n, and a have the same meanings as those in formula (1). ６ 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 —C(CH ３ ) = CH ２ In addition, R ６ reacts with SiH in the above formula (3) to form R ５ It is a group that

[0025] 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, it becomes easier to remove the unreacted compound represented by formula (3) 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, among which trimethoxysilane and triethoxysilane are more preferred.

[0026] 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 commonly used in hydrosilylation reactions. For example, platinum alone or a platinum-based catalyst such as platinum supported on a support such as alumina, silica, or carbon black can be used. 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 because the compound represented by formula (3) is generally volatile and hydrolyzable, it is preferable to use an inert gas-sealed environment. The compounding ratio of the compound represented by formula (3) and the compound represented by formula (4) is 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 volatilization, thereby reducing the amount of impurities in the resin composition. Furthermore, the compounding ratio of the compound represented by formula (3) and 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) per mole of the reactive alkenyl group in the compound represented by formula (4).

[0027] The temperature at which the compound represented by formula (3) is removed by heating may be 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 removing by heating the compound represented by formula (3), the compound may be removed by heating under a reduced pressure environment as described above, or may be removed under reduced pressure without heating. When removing by heating under a reduced pressure environment, the heating temperature may be within the above range, or may be below the lower limit of the above temperature range.

[0028] 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 in the above formulas (3) and (5) １ , R ２ , R ３ , R ５ , n, and a have the same meanings as those in formula (1). ６ is an alkenyl group having 2 to 10 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms, and more preferably —C(CH ３ ) = CH ２ In addition, R ６ reacts with SiH in the above formula (3) to form R ５ It is a group that

[0029] The reaction conditions, such as the catalyst, reaction temperature, reaction time, and solvent used in the reaction in the presence of a 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) to 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). The excess amount allows the compound represented by formula (5) 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 volatilization, 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 (5) is preferably such that the amount of reactive hydrogen groups in the compound represented by formula (3) is 1.2 moles or more, and even more preferably 1.2 moles or more and 2.5 moles or less, per mole of reactive alkenyl groups 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.

[0030] During the production of the (B) compound in the present invention, impurities other than the (B) compound may be generated, or components other than the (B) compound 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 decompression, and by-products generated during the synthesis of the (B) compound. In the present production method, a step of further removing or reducing impurities may be carried out after the steps described above. However, from the perspective of simplifying the process, the step of removing or reducing impurities may not be carried out. Furthermore, since the (B) compound can be produced by a method that can suppress the amount of impurities as described above, a high-purity (B) compound can be produced without 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 high-quality resin compositions and heat-dissipating materials can be consistently provided. Furthermore, oil bleeding due to impurities is suppressed. The smaller the amount of impurities, the better, and 0 parts by mass is particularly preferred relative to 100 parts by mass of the produced (B) compound. 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 relative to 100 parts by mass of the produced (B) compound.

[0031] <(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 above-described (B) compound, thereby improving dispersibility in the resin composition or in the cured resin composition and 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.

[0032] 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 is surface-treated with the (B) compound described above, has improved dispersibility in the resin composition, and is easy to improve thermal conductivity.

[0033] 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.

[0034] (C) The thermally conductive filler preferably contains two or more types of particles with different average primary particle sizes. When two or more types of particles with different average primary particle sizes are used, the particles with smaller average particle sizes are inserted between the particles with larger average particle sizes, which makes it easier to properly disperse the thermally conductive filler in at least one of the silicone resin and the silicone oil while increasing the loading rate of the thermally conductive filler. Note that the resin composition can be determined to contain two or more types of particles with different average primary particle sizes when two or more peaks appear in the particle size distribution of the thermally conductive filler.

[0035] (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 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 thermally conductive filler). Furthermore, it is also preferable that the large-particle thermally conductive filler contains two or more types of particles with different average primary particle diameters.

[0036] (C) The types of thermally conductive filler that can be used include those described above. As described above, the thermally conductive filler is preferably at least one selected from the group consisting of alumina, diamond, and aluminum nitride.

[0037] <Alumina> When alumina is used as the (C) thermally conductive filler, it is preferable to include two or more types of particles having different average particle diameters of primary particles. When two or more types of particles having 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 appropriately disperse the alumina in the silicone resin and increase the alumina filling rate.

[0038] When the alumina contains two or more types of particles having different average primary particle sizes, the alumina is preferably a mixture of particles having 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 having 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").

[0039] When the alumina contains both small particle size alumina and large particle size alumina, the mass ratio of the large particle size alumina to the small particle size alumina (large particle size / small particle size) is, for example, 0.1 to 50, preferably 1 to 15, and more preferably 5 to 15. With such a mass ratio, the alumina is easily filled into at least one of the silicone resin and the silicone oil, and thermal conductivity is likely to be good.

[0040] The large particle size alumina has an average primary particle size of preferably 12 μm to 100 μm, more preferably 15 μm to 80 μm, and the small particle size alumina has an average primary particle size of preferably 0.2 μm to 5 μm, more preferably 0.2 μm to 3 μm.

[0041] <Diamond> When diamond is used as (C) 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 diamond filling rate is easily increased.

[0042] When the diamond contains two or more types of particles with different average primary particle diameters, it is preferable that the diamond is 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 particle diameter 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 particle diameter diamonds").

[0043] When the diamond contains both small-sized diamonds 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 the silicone oil, and thermal conductivity is likely to be good.

[0044] 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. This makes it easier for the diamond to be filled with at least one of the silicone resin and the silicone oil, resulting in better thermal conductivity.

[0045] The small-diameter diamond preferably has an average primary particle size of 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 the silicone oil, resulting in better thermal conductivity.

[0046] <Aluminum Nitride> When aluminum nitride is used as the (C) thermally conductive filler, it is preferable to contain two or more types of particles whose primary particles have different average 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.

[0047] When aluminum nitride contains two or more types of particles having different average primary particle sizes, the aluminum nitride is preferably a mixture of particles having 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 having 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").

[0048] When the aluminum nitride contains both small particle size aluminum nitride and large particle size aluminum nitride, the mass ratio of the large particle size aluminum nitride to the 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, and thermal conductivity is likely to be good.

[0049] The large-particle-size aluminum nitride preferably has an average primary particle size of 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. This makes it easier for the aluminum nitride to be filled with at least one of the silicone resin and the silicone oil, resulting in better thermal conductivity.

[0050] The small particle size aluminum nitride preferably has an average primary particle size of 1 μm or more and 8 μm or less, 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.

[0051] When the resin composition contains the 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 more than these lower limits, the thermal conductivity of the resin composition and its cured product is easily improved.

[0052] Furthermore, the (C) thermally conductive filler of the present invention can be surface-treated using the (B) compound as described above. The surface-treated thermally conductive filler can be obtained by mixing the (B) compound and the (C) thermally conductive filler. Furthermore, from the viewpoint of facilitating the surface treatment during mixing, it is preferable to use a wet treatment method, a dry treatment method, or the like. In the wet treatment method, for example, the (C) thermally conductive filler is added to a solution in which the (B) compound is dispersed or dissolved, and mixed, followed by heat treatment to bond or adhere the (B) compound to the surface of the thermally conductive filler. The dry treatment method is a surface treatment method that does not use a solution. Specifically, the (C) thermally conductive filler and the (B) compound are mixed and stirred in a mixer or the like, and then heat treated to bond or adhere the (B) compound to the surface of the thermally conductive filler. The surface treatment performed by mixing the thermally conductive filler (C) and the compound (B) can also be performed in the presence of at least one of the silicone resin (A) and silicone oil (described later). 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).

[0053] <(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.

[0054] (Silicone Resin) The type of silicone resin is not particularly limited, but condensation curable silicone resins and addition reaction curable silicone resins are preferred, and addition reaction curable silicone resins are more preferred.

[0055] The addition reaction curable silicone resin preferably comprises a silicone compound as a base component and a curing agent that cures the base component. The silicone compound used as the base component is preferably an organopolysiloxane having an alkenyl group. Examples of alkenyl groups include those having 2 to 6 carbon atoms, such as vinyl groups, allyl groups, 1-butenyl groups, and 1-hexenyl groups, with vinyl groups being preferred from the standpoint of ease of synthesis and cost. The silicone compound used as the base component may have one or more alkenyl groups, but generally has two or more.

[0056] Specific examples of organopolysiloxanes having alkenyl groups include organopolysiloxanes terminated at both vinyl ends, such as polydimethylsiloxane terminated at both vinyl ends, polyphenylmethylsiloxane terminated at both vinyl ends, a copolymer of dimethylsiloxane and diphenylsiloxane terminated at both vinyl ends, a copolymer of dimethylsiloxane and phenylmethylsiloxane terminated at both vinyl ends, and a copolymer of dimethylsiloxane and diethylsiloxane terminated at both vinyl ends. The silicone compound used as the base agent may have a viscosity at 25°C of 1,000 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.

[0057] 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, organohydrogenpolysiloxanes, which are organopolysiloxanes having two or more hydrosilyl groups (SiH), are preferred. Examples of organohydrogenpolysiloxanes include methylhydrosiloxane-dimethylsiloxane copolymers, polymethylhydrosiloxanes, polyethylhydrosiloxanes, and methylhydrosiloxane-phenylmethylsiloxane copolymers. These may or may not contain hydrosilyl groups at their terminals. The viscosity of the curing agent at 25°C is preferably 1,000 mPa·s or less, preferably 50 mPa·s or more, more preferably 100 mPa·s or more but 900 mPa·s or less, and even more preferably 100 mPa·s or more but 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.

[0058] Furthermore, when using a silicone resin, a curing catalyst is usually blended. Examples of the curing catalyst include platinum-based catalysts, palladium-based catalysts, and rhodium-based catalysts, with platinum-based catalysts being preferred among these. The curing catalyst is a catalyst for curing the silicone compound and curing agent, which are the raw materials for the silicone resin. The blending amount of the curing catalyst 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.

[0059] The silicone resin may be either a one-component curing type or a two-component curing type. In the two-component curing type, the first component containing the base resin and the second component containing the curing agent are mixed to prepare a resin composition. 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, it is preferable to use a compound represented by general formula (1) and a compound represented by general formula (2) together as the (B) compound, as this is more effective than using each compound alone, and is desirable from the viewpoint of suppressing voids that occur when the compound is left standing at high temperatures after application, and is effective for one-component non-curing heat-dissipating compounds.

[0060] (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 having reactive groups as long as it is liquid, or a reaction product of a reactive silicone. It may also be a mixture of various silicone oils. Examples of silicone oils 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 oil, aralkyl-modified silicone oil, fluoroalkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher fatty acid amide-modified silicone oil, and phenyl-modified silicone oil.

[0061] 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.

[0062] The content of at least one of the (A) silicone resin and the (A) 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, relative to 100 parts by mass of the (C) thermally conductive filler.

[0063] 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 improving the dispersibility of the (C) thermally conductive filler in at least one of the (A) silicone resin and the silicone oil. Alternatively, the (B) compound and the (C) thermally conductive filler may be first mixed together, allowing the (B) compound to adhere to or react with the surface of the (C) thermally conductive filler, and then at least one of the (A) silicone resin and the silicone oil may be further mixed to prepare the resin composition. Alternatively, as described above, the resin composition may be prepared by mixing the first and second liquids prepared in advance. The first and second liquids may also be prepared by mixing the various components in the same manner.

[0064] 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 at least one of (A) a silicone resin and a silicone oil, and a (B) compound. The resin composition containing at least one of (A) a silicone resin and a silicone oil, and a (B) compound can be used as a filling composition for (C) a thermally conductive filler, and can be used by appropriately blending the (C) thermally conductive filler.

[0065] The resin composition of the present invention may contain additives such as antioxidants, heat stabilizers, colorants, flame retardants, and antistatic agents, if necessary.

[0066] 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 other means 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 this case, the electronic device can include an electronic component and a 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 by the electronic component.

[0067] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0068] The samples prepared in each example and comparative example were evaluated as follows: When a silicone resin was used as component (A), the magnitude of change in physical properties at high temperatures was evaluated by the "rate of change in hardness," and when a silicone oil was used as component (A), the magnitude of change in physical properties at high temperatures was evaluated by the "rate of change in viscosity" or "rate of change in piercing load."

[0069] [Rate of change in hardness] The rate of change in hardness was calculated from the initial hardness of the cured products of the resin compositions 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: Rate of change in hardness (%) = [(Hardness after heat treatment - Initial hardness) / Initial hardness] x 100. Note that the hardness was measured using an automatic hardness measuring device, "GX-02E" manufactured by Teclock Corporation, to measure Type E hardness.

[0070] [Viscosity Change Rate] The viscosity change rate was calculated from the initial viscosity of the resin compositions produced 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 measuring device used was an "HB DVE" manufactured by Eiko Seiki Co., Ltd.

[0071] [Penetration Load Change Rate] The penetration load change rate was calculated from the initial penetration load of the resin compositions produced in Examples 10 to 19, 23 to 26 and Comparative Examples 14 to 17, 19 to 28, and 30 to 33 and the penetration load after heat treatment at 150°C for 200 hours, using the following formula: Penetration Load Change Rate (%) = [(Penetration Load After Heat Treatment - Initial Penetration Load) / Initial Penetration Load] x 100 The penetration load was measured by piercing the sample with a needle and measuring the load when it reached a depth of 6 mm from the surface. The penetration load was measured using a penetration load measuring machine, a digital force gauge "ZTS-5N" manufactured by IMADA, and the indentation was measured under the conditions of a needle diameter of 1 mm, an indentation speed of 10 mm / min, and a measurement temperature of 23°C.

[0072] [Thermal Conductivity] The thermal conductivity was measured at 23°C in accordance with ASTM D5470. The measurement was performed using a "T3Ster DynTIM Tester" manufactured by Mentor, a Siemens Business. [Condition] Measurement was performed in accordance with JIS K-2220 using a quarter cone. [Void Fraction] 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. The substrate was stored in this fixed state at 150°C for 24 hours. The void fraction 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 fraction was judged according to the following criteria. A... Void fraction is 10% or less B... Void fraction is more than 10% and less than 15% C... Void fraction is more than 15% and less than 20%

[0073] [Oil Bleeding] 0.5 g of the paste-like resin composition was applied to a frosted glass, and the distance of oil seeping out after 24 hours at 150°C was measured. <Judgment Criteria> The oil bleeding was evaluated according to the following criteria: A: Bleeding distance 2 mm or less B: Bleeding distance more than 2 mm and less than 3 mm C: Bleeding distance more than 3 mm

[0074] The components used in each example and comparative example are as follows: <Component (A): Silicone Resin> Addition reaction type silicone resin Base agent: Organopolysiloxane with vinyl groups at both ends (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)

[0075] <(B) Compound> "Treatment agent 1," "Treatment agent 2," "Treatment agent 3," "Treatment agent 5," and "Treatment agent 6" were prepared as compounds represented by general formula (1), and "Treatment agent 4" was prepared as a compound represented by general formula (2), and were used as follows.

[0076] [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, followed by the addition of nitrogen. The reactor was sealed and heated at 70°C for 2 hours. The lid of the reactor was then opened, and the reactor was heated at 150°C for 0.5 hours with the lid open, thereby producing Treatment Agent 1. During the above charging, triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "MCR-M17" were blended so that there were 2 moles of reactive hydrogen groups in the triethoxysilane per 1 mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight. The reaction formula is as follows, and in this reaction formula, n is 55 to 75.

[0077] [Production 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.

[0078] [Production of Treatment Agent 3] Trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), Gelest's "MCR-M17," and hydrosilylation agent were charged into a reactor, followed by the addition of nitrogen. The reactor was sealed and heated at 50°C for 3 hours. The lid of the reactor was then opened, and the reactor was heated at 100°C for 0.5 hours with the lid open to produce Treatment Agent 3. During the above charging, trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "MCR-M17" were blended so that there were 2 moles of reactive hydrogen groups in trimethoxysilane per 1 mole of reactive alkenyl groups in "MCR-M17" calculated from the molecular weight. The reaction formula is as follows, and in this reaction formula, n is 55 to 75.

[0079] [Production of Treatment Agent 4] Triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), Gelest's "DMS-R18," and hydrosilylation agent were charged into a reactor, followed by the addition of nitrogen. The reactor was sealed and heated at 70°C for 2 hours. The reactor lid was then opened, and the reactor was heated at 150°C for 0.5 hours with the lid open to produce Treatment Agent 4. During the above charging, triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and "DMS-R18" were blended so that 2 moles of reactive hydrogen groups in triethoxysilane were present per 1 mole of reactive alkenyl groups in "DMS-R18" calculated from the molecular weight. The reaction formula is as follows, and in this reaction formula, n is 50 to 70. The above treatment agents 1, 2 and 4 are １ Identified by H-NMR. １ H-NMR (CDCl ３ ), device name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4T, temperature 25°C, sample concentration 10wt%, number of integrations 8 times: δ 4.02ppm (m, 2H, -COO-CH ２ -), 3.82ppm (q, J = 6.8Hz, 6H, -Si-O-CH ２ -), 2.65ppm (m, 1H, -OCO-CH-), 1.65ppm (m, 2H, -COOCH ２ -CH ２ -), 2.32ppm (m, 4H, -SiCH２ -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)-), 0.88ppm (t, J=7.2Hz, 3H-SiC ２ H ６ -CH ３ ), 0.77ppm (dd, J=7.2, 14.2Hz, 1HOCOCH(CH ３ )CH-H-), 0.54ppm(m,4H,-Si-CH ２ -C ３ H ７ / -COOC ２ H ４ -CH ２ -) 0.08ppm (m, 436H, -Si-(CH ３ ) ２ )

[0080] [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.

[0081] [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, and therefore will not be described here.

[0082] The compounds used in the comparative examples, "treatment agent 7," "treatment agent 8," and "treatment agent 11," were prepared as follows and used.

[0083] [Production of Treatment Agent 7] Treatment agent 7 was obtained by reacting "KBM-503" manufactured by Shin-Etsu Silicones Co., Ltd. with "MCR-H11" manufactured by Gless Co., Ltd. in the presence of a hydrosilylation catalyst. 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 formula is as follows, and in this reaction formula, n is 5 to 6.

[0084] [Production of Treatment Agent 8] Treatment agent 8 was produced in the same manner as treatment agent 7, except that "MCR-H21" manufactured by Gelest was used instead of MCR-H11. The reaction scheme is the same as that for the production of treatment agent 7, and therefore will not be described here.

[0085] [Preparation of Treatment Agent 11] Treatment agent 11 was prepared in the same manner as treatment 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 above treatment agents 7, 8 and 11 are ２９ Si-NMR, １ Identified by H-NMR. １ H-NMR (CDCl ３ ), device name: AVANCE400 (manufactured by Bruker), magnetic field strength 9.4T, temperature 25°C, sample concentration 10wt%, number of integrations 8 times: δ 4.70-4.66ppm (m, 1H, HSi), 3.56ppm (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), 0.17-0.02ppm(m, 18H, Si(CH ３ ) ２ O).

[0086] Furthermore, the compounds used in the comparative examples were "treatment agent 9," "treatment agent 10," and "decyltrimethoxysilane," which have the following structures.

[0087] [Treatment agent 9] n is 8 to 10. [Treatment Agent 10] This is a compound having the structure of the above-mentioned treatment agent 9, where n is 60 to 80.

[0088] [Decyltrimethoxysilane]

[0089] <(C) Component: 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 aluminas 1 to 4, diamonds 1 to 7, and aluminum nitrides 1 to 4 are the average particle diameters of primary particles.

[0090] Example 1 To 5.2 parts by mass of vinyl-terminated organopolysiloxane (viscosity at 25°C: 300 mPa·s) constituting the main component of the addition reaction type silicone resin, (B) compound and (C) thermally conductive filler were added as dispersants in the amounts shown in Table 1, and 1.5 parts by mass of a reaction retarder and a catalytic amount of a platinum catalyst were added to prepare a first liquid of the resin composition. Furthermore, to 5.2 parts by mass of organohydrogenpolysiloxane (viscosity at 25°C: 400 mPa·s) constituting the curing agent of the addition reaction type silicone resin, (B) compound and (C) thermally conductive filler were added as dispersants in the amounts shown in Table 1, to prepare a second liquid of the resin composition. The first liquid and the second liquid were mixed in a mass ratio (first liquid / second liquid) of 1:1, and then poured into a mold and heated at 70°C for 1 hour to allow the curing reaction to proceed. The cured product of the resin composition obtained was stored at 23° C. for 12 hours, and the time point at which no change in hardness was observed was evaluated as the initial hardness of the cured product of the resin composition.

[0091] 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.

[0092] [Examples 10 to 26, Comparative Examples 14 to 33] Paste-like resin compositions were prepared by mixing silicone oil, a thermally conductive filler, and a dispersant according to the formulations shown in Table 2. The resin compositions were heated at 150°C for 1 hour, and the state after standing at 23°C for 12 hours was evaluated as the initial state. [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 formulations shown in Table 3. The void fraction of the prepared resin compositions was calculated at room temperature and after 24 hours at 150°C.

[0093] [Examples 30 to 32] Treating agent 1 was prepared in three batches by changing the material lot and scale so that the mass parts per batch were as shown in Table 4. The purity and impurity concentration were measured 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%, number of accumulations 8), and the remaining amounts of triethoxysilane, MCR-M17, non-reactive impurities, MCR-H11, and KBM503 were determined.

[0094] Comparative Examples 39 to 44 Six batches of treating agent 7 were prepared by changing the material lot and scale so that the mass parts per batch were as shown in Table 4. The purity and impurity concentration were measured 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%, number of accumulations 8), and the remaining amounts of triethoxysilane, MCR-M17, non-reactive impurities, MCR-H11, and KBM503 were determined.

[0095] [Examples 33 to 37, Comparative Examples 45 to 50] In accordance with the method of Example 1, the effects of each treatment agent on hardness were measured using the formulations shown in Table 5.

[0096] [Examples 38 to 42, Comparative Examples 51 to 53] Paste-like resin compositions were prepared by mixing silicone oil, a thermally conductive filler, and a dispersant according to the formulations shown in Table 6. The resin compositions were 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 frosted glass, and the amount of oil seeping out after 24 hours at 150°C was evaluated.

[0097]

[0098]

[0099]

[0100]

[0101] *The treatments in Table 5 are as follows: Treatment 1 (Lot #1) → Treatment 1 prepared in Example 30 Treatment 1 (Lot #2) → Treatment 1 prepared in Example 31 Treatment 1 (Lot #3) → Treatment 1 prepared in Example 32 Treatment 7 (Lot #1) → Treatment 7 prepared in Comparative Example 39 Treatment 7 (Lot #2) → Treatment 7 prepared in Comparative Example 40 Treatment 7 (Lot #3) → Treatment 7 prepared in Comparative Example 41

[0102]

[0103] 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 incorporating the (B) compound into silicone oil, using a compound having trialkoxy groups at both ends of the silicone chain, as in the structure of formula (2), can produce a resin composition with superior performance. This demonstrates that the resin composition of the present invention using a (B) compound with 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, resin compositions using compounds without a specific structure have unstable impurity levels, even when using the same type of compound. Furthermore, the performance of the resin composition varies significantly depending on the compound used, resulting in unstable quality.

Claims

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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different, a is an integer of 0 to 2, and n is an integer of 4 to 150.

2. The resin composition according to claim 1, wherein the thermally conductive filler (C) 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 claim 1 or 2, wherein the thermally conductive filler (C) is at least one selected from the group consisting of alumina, diamond, and aluminum nitride.

4. 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.

5. The resin composition according to claim 1 or 2, 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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different, a is an integer of 0 to 2, and n is an integer of 4 to 150.

7. The compound (B) according to claim 6, which is used as a dispersant.

8. A thermally conductive filler surface-treated with the compound (B) according to claim 6 or 7.

9. A resin composition comprising (A) at least one of a silicone resin and a silicone oil, and (B) the compound according to claim 6 or 7.

10. A heat dissipation member formed from the resin composition according to claim 1 or 2.

11. An electronic device comprising an electronic component and the heat dissipation member according to claim 10 disposed on the electronic component.

12. 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 a plurality of R １ may be the same or different, R ２ is an alkyl group having 1 to 4 carbon atoms, and R ２ When there are multiple R ２ may be the same or different, 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 R ３ When there are multiple R ３ may be the same or different, R ４ is an alkyl group having 1 to 8 carbon atoms, and R ５ is an alkylene group having 2 to 20 carbon atoms, and a plurality of R ５ may be the same or different, a is an integer of 0 to 2, n is an integer of 4 to 150, R ６ is an alkenyl group having 2 to 20 carbon atoms, which reacts with SiH in the above formula (3) to form R ５ It is a group that 13. A 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).

14. The method for producing compound (B) according to claim 12 or 13, wherein the compound represented by general formula (3) is removed after the completion of the hydrosilylation reaction.

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