Thermal conductive curable silicone composition, cured product or gap filler obtained by curing the composition, two-component silicone composition set for obtaining the composition, and method for producing the composition

Abstract

containing components (a) to (g): (a) a linear organopolysiloxane compound having 1.5 to 2.0 alkenyl groups at its ends (b) a thermally conductive filler (c) an alkyltrialkoxysilane compound (d) a condensation reaction catalyst (e) a hydrosilylation reaction catalyst (f) an organosilicon compound represented by the following general formula (1) JPEG0007708994000028.jpg50159R 1 is an alkenyl group or -(CH2) m -Si(OR 3 )3, R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms, n is an integer of 3 to 8, and m is an integer of 0 to 8. (g) an organopolysiloxane compound having 1.5 or more hydrosilyl groups in the molecule component (f) is 0.5 to 10 parts by mass with respect to 100 parts by mass of component (a), the content of component (b) in the composition is 60 to 82% by volume, component (c) is 0.1 to 1.5 parts by mass with respect to 100 parts by mass of component (b), the molar amount of the hydrosilyl group in component (g) with respect to the molar amount of the alkenyl group in component (a) is 0.5 to 5.0, a thermally conductive curable silicone composition.

Description

Technical Field

[0001] The present invention relates to a thermally conductive curable silicone composition, a cured product or a gap filler obtained by curing the composition, a two-component silicone composition set for obtaining the composition, and a method for producing the composition.

Background Art

[0002] As the electrification of transportation vehicles such as automobiles, ships, and aircraft progresses, in order to extend the cruising range, the demand for higher capacity or higher output of the batteries installed in transportation vehicles is increasing day by day. When the current value increases due to the higher capacity or higher output of the battery, the amount of heat generated also increases. Therefore, the importance of thermally conductive members (gap fillers, thermally conductive sheets, thermal greases, etc.) for efficiently transferring the heat generated by the battery to a heat dissipation member such as a heat sink is increasing. A gap filler is an adhesive thermally conductive filling material that fills the space between the battery and the heat dissipation member, and can be formed by applying or filling a slurry-like or paste-like curable composition containing a thermally conductive filler to the location where the gap filler is disposed and then subjecting it to a curing reaction.

[0003] Due to the higher capacity or higher output of the battery, the degree of expansion and contraction (volume change) of the battery accompanying charge and discharge is increasing day by day. In addition, when the transportation vehicle is running, the inside of the transportation vehicle is exposed to continuous vibrations of various magnitudes. Therefore, the above-mentioned gap filler is required to have high adhesiveness and high flexibility that can continuously follow the large volume change of the battery and can also withstand the shear force and load change accompanying the repeated vibrations.

[0004] For example, in Patent Document 1, (A) a diorganopolysiloxane having an alkenyl group bonded to a silicon atom, (D) an addition catalyst, (E) a thermally conductive filler, and (F) a condensation catalyst, and a first liquid containing the same, (A) A diorganopolysiloxane having an alkenyl group bonded to a silicon atom, (B) a diorganopolysiloxane having a hydrogen atom bonded to a silicon atom, (C) an organosilicon compound having at least two groups selected from (C-1) a methoxy group and an ethoxy group and having no hydrocarbon group or vinyl group having 3 or more carbon atoms, and at least one selected from (C-2) a hydrolyzate of the organosilicon compound (C-1), and (E) a heat conductive filler, and a second liquid A two-component heat conductive silicone composition prepared so that each component has a specific amount is described. And Patent Document 1 discloses that a heat conductive silicone composition obtained by mixing the above first liquid and second liquid is applied to at least one base material of a battery unit housing and a cooler, and then cured to form a gap filler. This gap filler is described as having good storage stability, being able to maintain good adhesiveness even under vibration conditions with respect to the base material, and also having excellent heat dissipation characteristics.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] When the inventors studied the two-component heat conductive silicone composition or gap filler described in Patent Document 1, in order to continuously exhibit efficient heat dissipation from a high-capacity and high-output battery installed in a transportation machine, neither adhesiveness nor flexibility was sufficient. That is, when exposed to repeated expansion and contraction of the battery or repeated vibration over a long period of time, it is difficult to maintain sufficient followability with respect to an adherend such as a battery unit housing, and the gap filler may peel off from the adherend, or damage such as cracks or defects may occur in the gap filler.

[0007] An object of the present invention is to provide a cured product (gap filler) that is difficult to peel off from an adherend and is less likely to be damaged even when repeatedly exposed to the expansion, contraction, and vibration of the adherend, and that can continuously exhibit high-efficiency heat dissipation even when repeatedly running in a state installed on a transporter. Another object of the present invention is to provide a thermally conductive curable silicone composition suitable for forming the cured product, and a two-component silicone composition set for obtaining this composition.

Means for Solving the Problems

[0008] The above problems of the present invention are solved by the following means. 〔1〕 A thermally conductive curable silicone composition, The thermally conductive curable silicone composition contains the following components (a) to (g): (a) A linear organopolysiloxane compound having 1.5 to 2.0 alkenyl groups at the molecular chain terminals and no hydrosilyl group; (b) A thermally conductive filler; (c) An alkyltrialkoxysilane compound; (d) A condensation reaction catalyst; (e) A hydrosilylation reaction catalyst; (f) An organosilicon compound represented by the following general formula (1);

Chemical formula

[10] The two-component silicone composition set according to [9], wherein the first liquid contains at least the components (a) to (e), and the second liquid contains at least the components (a) to (c), (f), and (g).

[11] A method for producing a thermally conductive curable silicone composition according to any one of [1] to [5], which includes mixing the first liquid and the second liquid of the two-component silicone composition set according to [9] or

[10] .

[12] The method for producing a thermally conductive curable silicone composition according to

[11] , which includes blending a mixture of the component (b) and the component (c) in the preparation of the first liquid and / or the preparation of the second liquid.

[0009] In the present invention, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. [Advantages of the Invention]

[0010] The cured product (gap filler) of the present invention is difficult to peel off from the adherend and is less likely to be damaged even when repeatedly exposed to the expansion, contraction, and vibration of the adherend, and can continuously exhibit high-efficiency heat dissipation even when repeatedly running in a state installed in a transport machine. The thermally conductive curable silicone composition of the present invention can obtain the above cured product (gap filler) by subjecting this composition to a curing reaction. Further, the two-component silicone composition set of the present invention can obtain the thermally conductive curable silicone composition of the present invention by mixing the two components, and the above cured product (gap filler) can be obtained by subjecting this composition to a curing reaction.

Mode for Carrying Out the Invention

[0011] Preferred embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments except as defined in the present invention.

[0012] [Thermally Conductive Curable Silicone Composition] The thermally conductive curable silicone composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains at least the following components (a) to (g) in specific amounts. The composition of the present invention can contain components other than the following components (a) to (g) as long as the effects of the present invention are not impaired. The composition of the present invention is in a state before the curing reaction progresses, and therefore is usually a fluid dispersion at room temperature (25°C), and at least the thermally conductive filler is dispersed as solid particles. The components contained or that can be contained in the composition of the present invention will be described.

[0013] [Component (a) A linear organopolysiloxane compound having 1.5 to 2.0 alkenyl groups at the molecular chain terminals and no hydrosilyl group> Component (a) is a linear organopolysiloxane having 1.5 to 2.0 alkenyl groups at the molecular chain ends and no hydrosilyl groups. "Linear" means that the linking structure by siloxane bonds is linear (chain-like), and "molecular chain ends" means the ends of the chain. Therefore, the structure in which one molecule of the linear organopolysiloxane compound has alkenyl groups at its molecular chain ends includes two types: a structure having an alkenyl group at one end (in this case, the number of alkenyl groups in one molecule is 1) and a structure having alkenyl groups at both ends (in this case, the number of alkenyl groups in one molecule is 2). "Having 1.5 to 2.0 alkenyl groups at the molecular chain ends" means that the value obtained by dividing (dividing) the total number of alkenyl groups at the molecular chain ends of all molecules of the "linear organopolysiloxane having alkenyl groups at the molecular chain ends and no hydrosilyl groups" (all molecules constituting component (a)) contained in the composition of the present invention by the number of all such molecules (i.e., the average value) is 1.5 to 2.0. In component (a), the number of alkenyl groups at the molecular chain ends is preferably 1.6 to 2.0, more preferably 1.7 to 2.0, and also preferably 1.8 to 2.0. In addition, the linear organopolysiloxane having 1.5 to 2.0 alkenyl groups at the molecular chain ends and no hydrosilyl groups, which is component (a), preferably has 1.5 to 50 alkenyl groups in the molecule (the whole molecule), more preferably 1.6 to 20 alkenyl groups, still more preferably 1.7 to 10 alkenyl groups, still more preferably 1.8 to 6 alkenyl groups, and also preferably 2 to 4 alkenyl groups. The number of alkenyl groups in this molecule is also the average value of the whole of component (a). Hereinafter, each molecule of the linear organopolysiloxane compound constituting component (a) is referred to as "(a) linear organopolysiloxane molecule".

[0014] (a) The linear organopolysiloxane molecule is linear with a main chain composed of repeating units of diorganosiloxy units (*-Si(R)2-O-*, where R is an organic group and * is a bonding site), and one or both of the two ends of this main chain are alkenyldialkylsiloxy groups (-Si(alkenyl)(alkyl)2; "alkenyl": alkenyl group, "alkyl": alkyl group). A linear diorganopolysiloxane molecule is preferred. In this case, for component (a) which is an aggregate of (a) linear organopolysiloxane molecules, the number of alkenyl groups at the molecular chain ends (the above average value) is 1.5 to 2.0 as described above. The above organic group R is preferably a hydrocarbon group having 1 to 18 carbon atoms. Preferred specific examples of the hydrocarbon group having 1 to 18 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-, pentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and aryl groups such as phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group; aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group, methylbenzyl group; groups in which some or all of the hydrogen atoms in these hydrocarbon groups are substituted by halogen atoms, cyano groups, etc. (for example, chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, cyanoethyl group), etc. The above organic group R is particularly preferably a methyl group. Also, it is preferable that a part of the above organic group R is an alkenyl group.

[0015] (a) A linear organopolysiloxane molecule may have an alkenyl group bonded not only to the terminal of the molecular chain but also to at least a part of Si constituting the siloxane bond in the main chain as described above. When using such a (a) linear organopolysiloxane molecule having crosslinking points other than the terminals, the three-dimensional network of the resulting cured product is formed more densely, which is advantageous for improving the shear adhesion strength. Conversely, when no alkenyl group is bonded to Si constituting the siloxane bond in the main chain, there is an advantage that the flexibility of the resulting cured product is increased due to fewer crosslinking points. (a) In the linear organopolysiloxane molecule, each siloxane unit constituting the molecule may be the same or different.

[0016] The viscosity of component (a) (an aggregate of (a) linear organopolysiloxane molecules) is not particularly limited, and for example, those having a viscosity of 10 to 10,000 mPa·s can be used. This clay preferably has a viscosity of 20 to 5000 mPa·s, and more preferably 30 to 2000 mPa·s. By setting the viscosity within the above range, the fluidity of the resulting thermally conductive curable silicone composition can be sufficiently ensured, the dischargeability is excellent, and the productivity of the cured product (gap filler) can be improved. Further, by setting the viscosity within the above range, the flexibility of the cured product of the thermally conductive curable silicone composition tends to be further increased.

[0017] The alkenyl group possessed by component (a) preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. Specific preferred examples of this alkenyl group include vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, etc., and the vinyl group is particularly preferred.

[0018] <Component (b) Thermally conductive filler> Component (b) is a particulate component that contributes to improving the thermal conductivity of the resulting cured product. As component (b), for example, a thermally conductive filler used in existing gap fillers can be used without particular limitation. In the composition of the present invention, the content of component (b) is 60 to 82% by volume, more preferably 63 to 77% by volume, and even more preferably 67 to 73% by volume.

[0019] Examples of the heat-conductive filler constituting component (b) include at least one filler such as metal, metal oxide, metal hydroxide, metal carbonate, metal nitride, and metal carbide. When forming a gap filler by curing the composition of the present invention and applying it to a battery for a transportation device (battery cell or battery module), in addition to excellent thermal conductivity, insulation is also required. Therefore, when assuming a gap filler applied to a battery for a transportation device, it is preferable to use ceramic particles or the like instead of conductive particles composed of the metal itself (carrier metal or alloy).

[0020] Examples of the material constituting the ceramic particles are as follows. Examples of the above metal oxides include aluminum oxide, zinc oxide, magnesium oxide, titanium oxide, silicon oxide, beryllium oxide, and the like. Examples of the above metal hydroxides include aluminum hydroxide, magnesium hydroxide, and the like. Examples of the above metal carbonates include magnesium carbonate, calcium carbonate, and the like. Examples of the above metal nitrides include aluminum nitride, silicon nitride, boron nitride, and the like. Examples of the above metal carbides include boron carbide, titanium carbide, silicon carbide, and the like.

[0021] Examples of the material of the conductive heat-conductive filler include graphite such as graphite and carbon, metals such as aluminum, copper, nickel, and silver, alloys composed of a combination of two or more metals, and mixtures thereof.

[0022] Among them, component (b) preferably contains at least one of aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, zinc oxide, aluminum nitride, and boron nitride, and more preferably contains at least one of aluminum hydroxide and aluminum oxide. Since a silicone composition using a thermally conductive filler with a high Mohs hardness may wear out the equipment during kneading and coating, from this perspective, it is preferable to use a thermally conductive filler with a low Mohs hardness. For example, aluminum hydroxide, which has a small specific gravity, is inexpensive, and has a low Mohs hardness, is suitable as component (b).

[0023] To more specifically describe the preferred form of component (b), it is preferable that the component (b) contains at least one of aluminum hydroxide and aluminum oxide, and the content of the component (b) in the thermally conductive curable silicone composition is preferably 60 to 82% by volume, and more preferably 67 to 73% by volume. By adjusting the component (b) in the composition in this way, while more effectively increasing the thermal conductivity of the resulting cured product, sufficient flexibility can also be ensured. Further, it is preferable that the component (b) contains aluminum hydroxide and the proportion of the aluminum hydroxide in the component (b) is 70% by volume or more. By incorporating the component (b) adjusted in this way into the composition, the adhesiveness can be further enhanced.

[0024] The particle size of the thermally conductive filler constituting component (b) is not particularly limited, and the particle size of the entire filler constituting component (b) is preferably 1 to 300 μm, more preferably 10 to 200 μm, still more preferably 20 to 150 μm, and still more preferably 25 to 120 μm. In the present invention, when simply referring to "particle size", it means the volume-based median diameter. By setting the particle size range in this way, while increasing the fluidity of the composition, even when the composition is thinly coated, the coating film is less likely to be blurred or rough. It is also preferable to use a combination of a plurality of thermally conductive fillers having different particle diameters and shapes. By doing so, the filling rate in the composition or cured product of the thermally conductive filler can be further increased, and the thermal conductivity of the cured product can be further enhanced. As an example, a form in which thermally conductive fillers having particle diameters of 100 μm, 10 μm, or 1 μm are combined and used can be mentioned. In this combination, the particle diameter (volume-based median diameter) of the entire filler constituting component (b) is preferably 10 to 90 μm, and more preferably 20 to 80 μm.

[0025] <Component (c) alkyltrialkoxysilane compound> The alkyltrialkoxysilane compound of component (c) modifies the surface of the thermally conductive filler by interacting with the surface of the thermally conductive filler of component (b) (for example, causing a dehydration condensation reaction with the hydroxyl groups on the surface). As a result, the dispersibility of the thermally conductive filler is improved, the increase in the viscosity of the composition of the present invention is suppressed, and the phenomenon of sedimentation of the thermally conductive filler over time can be suppressed, improving the handleability of the composition. For example, in the preparation of the composition or composition set of the present invention, the interactivity between component (b) and (c) can be further enhanced by premixing component (b) and (c) while heating and depressurizing as necessary. Also, in the preparation of the composition or composition set of the present invention, the surface modification efficiency of the thermally conductive filler, which is component (b), can be further enhanced by blending component (c) in a state dissolved in a solvent. From the perspective of being able to sufficiently and uniformly disperse the thermally conductive filler in the composition of the present invention, imparting sufficient fluidity to the composition, and further considering the perspective of sufficiently causing the interaction between the thermally conductive filler of component (b) and component (f) described later, in the composition of the present invention, with respect to 100 parts by mass of the content of component (b), the content of the said component (c) is 0.1 to 1.5 parts by mass.

[0026] The alkoxy group of the alkyltrialkoxysilane compound constituting component (c) preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group. Further, the alkyl group of the alkyltrialkoxysilane compound preferably has 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 3 to 18 carbon atoms, still more preferably 4 to 16 carbon atoms, still more preferably 5 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms. When the alkyl group has 3 or more carbon atoms, a straight chain is preferred.

[0027] Preferable specific examples of the alkyltrialkoxysilane compound constituting component (c) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, and the like.

[0028] <Component (d) Condensation Reaction Catalyst> Since the composition of the present invention contains the condensation reaction catalyst of component (d), sufficient adhesiveness to the adherend can be exhibited even under mild curing reaction conditions such as room temperature. Usually, condensation-reactive groups such as hydroxyl groups, alkoxy groups, and ester groups are present on the surface of adherends such as metal substrates such as aluminum and organic resin substrates such as PET. The condensation reaction catalyst of component (d) promotes the condensation reaction between the condensation-reactive groups on the surface of the adherend and the alkoxy groups, hydroxyl groups, etc. of the components constituting the composition of the present invention. The condensation reaction catalyst itself that can be used as component (d) is known, and known catalysts that function as this type of condensation reaction catalyst can be widely applied. For example, the condensation catalyst described as component (F) in Japanese Patent No. 7368656 is suitable as the condensation reaction catalyst of component (d) to be blended in the composition of the present invention. For example, one or more compounds (metal compounds) containing metal atoms selected from magnesium, aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, zirconium, tungsten, and bismuth can be used as component (d). Examples of such metal compounds include metal complex compounds. As the ligand constituting the metal complex compound, organic acids such as octylic acid, lauric acid, and stearic acid; alkoxides such as propoxide and butoxide; catechol; crown ether; polyvalent carboxylic acid; hydroxy acid; diketones such as ethyl acetoacetate; keto acid; and the like can be mentioned. A plurality of types of ligands may be bonded to one metal atom. Among them, complex compounds containing titanium, zirconium, or aluminum are preferable.

[0029] Specific preferable examples of the condensation reaction catalyst of component (d) are as follows. Examples of the alkoxy group-containing titanium compound (titanium alkoxide) include titanium tetramethoxide, titanium tetraethoxide, titanium tetraallyloxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-s-butoxide, titanium tetra-t-butoxide, titanium tetra-n-pentyloxide, titanium tetracyclopentyloxide, titanium tetrahexyloxide, titanium tetracyclohexyloxide, titanium tetrabenzyloxide, titanium tetraoctyloxide, titanium tetrakis(2-ethylhexyloxide), titanium tetradecyloxide, titanium tetra(lauryloxide), titanium tetrastearyloxide, titanium tetrabutoxide dimer, titanium tetrakis(8-hydroxyoctyloxide), titanium diisopropoxide bis(2-ethyl-1,3-hexanedionato), titanium bis(2-ethylhexyloxy) bis(2-ethyl-1,3-hexanedionato), titanium tetrakis(2-methoxyethoxide), titanium tetrakis(2-ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium butoxide triisopropoxide, titanium dibutoxide diisopropoxide, and titanium tetraphenoxide.

[0030] Examples of the titanium chelate compound include titanium dimethoxybis(ethylacetoacetate), titanium dimethoxybis(acetylacetonate), titanium diethoxybis(ethylacetoacetate), titanium diethoxybis(acetylacetonate), titanium diisopropoxybis(ethylacetoacetate), titanium diisopropoxybis(methylacetoacetate), titanium diisopropoxybis(t-butylacetoacetate), titanium diisopropoxybis(methyl-3-oxo-4,4-dimethylhexanoate), titanium diisopropoxybis(acetylacetonate), titanium di-n-butoxybis(ethylacetoacetate), titanium di-n-butoxybis(acetylacetonate), titanium diisobutoxybis(acetylacetonate), titanium di-t-butoxybis(ethylacetoacetate), titanium di-t-butoxybis(acetylacetonate), titanium tetrakis(ethylacetoacetate), titanium tetrakis(acetylacetonate), titanium bis(trimethylsiloxy)bis(ethylacetoacetate), and titanium bis(trimethylsiloxy)bis(acetylacetonate).

[0031] Examples of the alkoxy group-containing zirconium compound include zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraallyloxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetraisobutoxide, zirconium tetra-s-butoxide, zirconium tetra-t-butoxide, zirconium tetra-n-pentyloxide, zirconium tetracyclopentyloxide, zirconium tetrahexyloxide, zirconium tetracyclohexyloxide, zirconium tetrabenzyloxide, zirconium tetraoctyloxide, zirconium tetrakis(2-ethylhexyloxide), zirconium tetradecyloxide, titanium tetradodecyloxide, zirconium tetrastearyloxide, zirconium tetrakis(2-methoxyethoxide), zirconium tetrakis(2-ethoxyethoxide), zirconium butoxidetrimethoxide, zirconium dibutoxidedimethoxide, zirconium butoxidetriethoxide, zirconium dibutoxidediethoxide, zirconium butoxidetriisopropoxide, zirconium dibutoxidediisopropoxide, and zirconium tetraphenoxide.

[0032] Examples of zirconium chelate compounds include zirconium tetra(acetylacetonate), zirconium dimethoxybis(ethylacetoacetate), zirconium dimethoxybis(acetylacetonate), zirconium diethoxybis(ethylacetoacetate), zirconium diethoxybis(acetylacetonate), zirconium diethoxybis(ethylacetoacetate), zirconium diisopropoxybis(ethylacetoacetate), zirconium triisopropoxy(ethylacetoacetate), zirconium tri-n-butoxide(ethylacetoacetate), zirconium diisopropoxybis(methylacetoacetate), zirconium diisopropoxybis(t-butylacetoacetate), zirconium diisopropoxybis(acetylacetonate), zirconium di-n-butoxybis(ethylacetoacetate), zirconium di-n-butoxybis(acetylacetonate), zirconium diisobutoxybis(ethylacetoacetate), zirconium diisobutoxybis(acetylacetonate), zirconium di-t-butoxybis(ethylacetoacetate), zirconium di-t-butoxybis(acetylacetonate), zirconium isopropoxytris(ethylacetoacetate), zirconium-n-butoxidetris(ethylacetoacetate), zirconium tetrakis(ethylacetoacetate), and zirconium tetrakis(acetylacetonate).

[0033] Examples of acylates containing zirconium include zirconium octylate and zirconium stearate.

[0034] Examples of the alkoxy group-containing aluminum compound include aluminum trimethoxide, aluminum triethoxide, aluminum triallyloxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-s-butoxide, aluminum tri-t-butoxide, aluminum tri-n-pentyloxide, aluminum tricyclopentyloxide, aluminum tridecyloxide, aluminum tridodecyloxide, aluminum tristearyloxide, aluminum tris(2-methoxyethoxide), aluminum tris(2-ethoxyethoxide), aluminum butoxidedimethoxide, aluminum methoxidedibutoxide, aluminum butoxidediethoxide, aluminum ethoxidedibutoxide, aluminum butoxidediisopropoxide, aluminum isopropoxidedibutoxide, and aluminum triphenoxide. Examples of aluminum chelate compounds include aluminum methoxybis(ethylacetoacetate), aluminum methoxydibis(acetylacetonate), aluminum ethoxybis(ethylacetoacetate), aluminum ethoxydibis(acetylacetonate), aluminum isopropoxybis(ethylacetoacetate), aluminum isopropoxybis(methylacetoacetate), aluminum isopropoxybis(t-butylacetoacetate), aluminum dimethoxybis(ethylacetoacetate), aluminum dimethoxybis(acetylacetonate), aluminum diethoxybis(ethylacetoacetate), aluminum diethoxybis(acetylacetonate), aluminum diisopropoxybis(ethylacetoacetate), aluminum diisopropoxybis(methylacetate), aluminum diisopropoxybis(t-butylacetoacetate), aluminum diisopropoxybis(methylacetoacetate), aluminum isopropoxybis(acetylacetonate), aluminum -n-butoxybis(ethylacetoacetate), aluminum -n-butoxybis(acetylacetonate), aluminum isobutoxybis(ethylacetoacetate), aluminum isobutoxybis(acetylacetonate), aluminum -t-butoxybis(ethylacetoacetate), aluminum -t-butoxybis(acetylacetonate), aluminum -2-ethylhexoxybis(ethylacetoacetate), aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and aluminum(acetylacetonate)bis(ethylacetoacetate).

[0035] In the composition of the present invention, the content of component (d) only needs to be used in an amount that functions as a catalyst (so-called catalytic amount). For example, based on 100 parts by mass of the content of component (a), the content of component (d) can be 0.1 to 10 parts by mass, preferably 0.2 to 8 parts by mass, more preferably 0.3 to 6 parts by mass, still more preferably 0.4 to 4 parts by mass, and preferably 0.6 to 3 parts by mass. In the case where component (d) is in a form in which a catalytically active substance is supported on a solid phase (supported catalyst), the content of the entire supported catalyst is defined as the content of component (d). This also applies to the following component (e).

[0036] <Component (e) Hydrosilylation reaction catalyst> The hydrosilylation reaction catalyst of component (e) is a component for promoting the hydrosilylation reaction (addition reaction) that occurs between the alkenyl group of component (a) and the hydrosilyl group of component (g). The hydrosilylation reaction catalyst itself that can be used as component (e) is known, and known catalysts that function as hydrosilylation reaction catalysts can be widely applied. For example, the addition catalyst described as component (D) in Japanese Patent No. 7368656 is suitable as the hydrosilylation reaction catalyst of component (e) to be blended in the composition of the present invention. For example, platinum group metals such as platinum, rhodium, palladium, osmium, iridium, and ruthenium are suitable as component (e). These metals can also constitute component (e) of the composition of the present invention in a state fixed to a particulate carrier material (for example, activated carbon, aluminum oxide, silicon oxide). In addition, as component (e), platinum halides, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-vinylsiloxane complexes, dicyclopentadiene-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, and other platinum compounds can be used. From the perspective of cost reduction, metal compound catalysts other than platinum group metals may be used as component (e). For example, iron-carbonyl complex catalysts, iron catalysts having a cyclopentadienyl group as a ligand, iron catalysts having a terpyridine-based ligand or a terpyridine-based ligand and a bistrimethylsilylmethyl group, iron catalysts having a bisiminopyridine ligand, iron catalysts having a bisiminoquinoline ligand, iron catalysts having an aryl group as a ligand, iron catalysts having a cyclic or acyclic olefin group having an unsaturated group, and iron catalysts having a cyclic or acyclic olefinyl group having an unsaturated group are suitable as component (e). In addition, cobalt catalysts, vanadium catalysts, ruthenium catalysts, iridium catalysts, samarium catalysts, nickel catalysts, manganese catalysts, etc. can also be used as component (e).

[0037] In the composition of the present invention, the content of component (e) only needs to be used in an amount that functions as a catalyst (so-called catalytic amount). For example, with respect to 100 parts by mass of the content of component (a), the content of component (e) is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass.

[0038] <Component (f) Organosilicon compound represented by general formula (1)> Component (f) is an organosilicon compound represented by the following general formula (1).

[0039]

Chemical formula

[0040] In the formula, two Rs 1 each independently represent an alkenyl group or -(CH2) m -Si(OR 3 )3. R 2 and R 3 represent an alkyl group having 1 to 4 carbon atoms. n is an integer of 3 to 8, and m is an integer of 0 to 8.

[0041] Component (f) is a component that enhances the adhesiveness between the base material (e.g., a battery cell, a battery module, a heat sink, etc.) to which the composition of the present invention is applied and the cured product obtained by curing the composition of the present invention applied on the base material.

[0042] The organosilicon compound of component (f) has at least one trialkoxysilyl group (-Si(OR 2 )3), and this trialkoxysilyl group undergoes hydrolysis in the presence of a condensation catalyst to generate a silanol group. The generated silanol group forms a hydrogen bond or a bond by a dehydration reaction with a hydroxyl group or the like present on the surface of the base material. Further, in the organosilicon compound of component (f), R 1 has a trialkoxysilyl group (-Si(OR 3 )3), or R 1 is an alkenyl group. When at least one of the two Rs 1 has a trialkoxysilyl group, in the presence of the condensation reaction catalyst of component (d), it is likely to undergo a hydrogen bond or a condensation reaction with the hydroxyl group present on the surface of the thermal conductivity filler of component (b). When at least one of Rs 1 is an alkenyl group, in the presence of the hydrosilylation reaction catalyst of component (e), it reacts with the hydrosilyl group of component (g) and functions as a crosslinking agent. Thereby, the adhesiveness between the composition of the present invention or its cured product and the base material is improved. In addition, in component (f), a medium-chain alkylene group having 3 to 8 carbon atoms (-(CH2) n -) is present. The presence of this partial structure imparts chemical structural flexibility to component (f) that functions as a crosslinking agent connecting the surface of the base material and the thermal conductivity filler or polysiloxane structure of component (b). As a result, flexibility is imparted to the adhesion interface or the vicinity thereof of the cured product obtained by curing the composition of the present invention. Therefore, even if a large strain occurs in the adhesion part due to the expansion and contraction of the battery or the vibration during running, the adhesive is less likely to be damaged and can maintain good adhesiveness over a long period. Further, since the number of carbon atoms of the above medium-chain alkylene group is 8 or less, the number of reactive groups per unit mass can be ensured, and a sufficient crosslinking point density can be obtained when cured, making the initial adhesiveness strong.

[0043] In the general formula (1), the organosilicon compound of component (f) has two Rs 1 both being -(CH2) m -Si(OR 3 )3 is also preferable, and both of the two Rs 1 being alkenyl groups are also preferable. Further, it is also preferable that one of the two Rs 1 is -(CH2) m -Si(OR 3 )3 and the other is an alkenyl group. R 1 The carbon number of the alkenyl group that can be adopted as is preferably 2 to 12, more preferably 2 to 10, still more preferably 2 to 8, further preferably 2 to 6, still further preferably 2 to 5, and particularly preferably 2 to 4. This alkenyl group is preferably linear. Specific preferable examples of this alkenyl group include a vinyl group, an allyl group, a 3-butenyl group, and the like. Further, in the general formula (1), m of -(CH2) 1 -Si(OR m )3 that can be adopted as R 3 is preferably 1 to 8, more preferably 2 to 8, and still more preferably 3 to 8. R 2 and R 3 are preferably alkyl groups having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

[0044] Preferred specific examples of the organosilicon compound of component (f) include 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, 1,3,5-tris(triethoxysilylpropyl)isocyanurate, 1-allyl-3,5-bis(trimethoxysilylpropyl)isocyanurate, 1-allyl-3,5-bis(triethoxysilylpropyl)isocyanurate, 1,3-diallyl-5-triethoxysilylpropyl isocyanurate, 1,3,5-tris(trimethoxysilylbutyl)isocyanurate, 1,3,5-tris(trimethoxysilylpentyl)isocyanurate, 1,3,5-tris(trimethoxysilylhexyl)isocyanurate, 1,3,5-tris(trimethoxysilylheptyl)isocyanurate, 1,3,5-tris(trimethoxysilyloctyl)isocyanurate, and the like.

[0045] When the composition of the present invention is cured, in order to achieve sufficient adhesion strength to substrates such as battery cells, battery modules, and heat sinks while sufficiently increasing the flexibility of the cured product, the content of component (f) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the content of component (a). The content of component (f) is preferably 0.6 to 9 parts by mass, more preferably 0.7 to 8 parts by mass, still more preferably 0.8 to 7 parts by mass, still more preferably 0.9 to 6 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the content of component (a).

[0046] <An organopolysiloxane compound having 1.5 or more hydrosilyl groups in the molecule and no alkenyl group in component (g)> Component (g) is an organopolysiloxane compound having 1.5 or more hydrosilyl groups in the molecule and no alkenyl group. "Having 1.5 or more hydrosilyl groups in the molecule" means that the total number of hydrosilyl groups possessed by all the molecules of "organopolysiloxane having a hydrosilyl group in the molecule and no alkenyl group" (all the molecules constituting component (g)) contained in the composition of the present invention, divided by the number of all the molecules (i.e., the average value) is 1.5 or more. Here, the "hydrosilyl group" means a functional group having a structure in which a hydrogen atom is directly bonded to a silicon atom. In the present invention, the number of "hydrosilyl groups" is the number of siloxane units having a hydrosilyl group, not the number of hydrogen atoms directly bonded to a silicon atom. Therefore, -SiH(R)-O- (R: substituent, preferably an organic group), -SiH2-O-, -SiH2(R), SiH(R)2, -SiH3 are all siloxane units, and the number of "hydrosilyl groups" is counted as 1. In the present invention, the "hydrosilyl group" preferably has one hydrogen atom directly bonded to a silicon atom, and an organic group is bonded to a bond of the remaining bonds of the silicon atom that does not form a siloxane bond. This organic group is preferably an alkyl group or an aryl group, more preferably an alkyl group. This alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably a methyl group or an ethyl group. Also, the above aryl group is preferably a phenyl group.

[0047] Component (g) is preferably an organopolysiloxane compound (organohydrogenpolysiloxane) having 1.5 to 50 hydrosilyl groups in the molecule, and the number of these hydrosilyl groups is more preferably 1.6 to 20, still more preferably 1.7 to 10, still more preferably 1.8 to 6, and still more preferably 2 to 4.

[0048] The viscosity of component (g) (which means the viscosity of the aggregate of organopolysiloxane molecules constituting component (g). The viscosity of component (g) is related to the degree of polymerization of the organopolysiloxane molecules constituting component (g)) is not particularly limited. For example, the viscosity of component (g) can be 10 to 10,000 mPa·s at 25°C. Component (g) is a component that serves as a curing agent for curing the composition of the present invention. In the molecule of the organopolysiloxane constituting component (g), the presence site of the hydrosilyl group is not particularly limited. For example, a structure in which hydrogen atoms are directly bonded to the silicon atoms at both ends of a linear diorganopolysiloxane molecule having a linking structure by a siloxane bond is preferable as the molecular structure of the organopolysiloxane constituting component (g). In this case, it is preferable that both ends are -SiH(R)2 (a structure in which one hydrogen atom is directly bonded to a silicon atom and organic groups are bonded to the remaining two bonds). In the organopolysiloxane molecule constituting component (g), the amount of the hydrosilyl group is preferably 0.01 to 10.0 mmol / g, more preferably 0.05 to 5.0 mmol / g, and even more preferably 0.5 to 2.0 mmol / g from the viewpoint of imparting practically sufficient strength and displacement followability to the composition of the present invention. Preferable specific examples of the organopolysiloxane molecule (organohydrogenpolysiloxane) constituting component (g) include, for example, methylhydrogenpolysiloxane, dimethylsiloxane·methylhydrogensiloxane copolymer, methylphenylsiloxane·methylhydrogensiloxane copolymer, cyclic methylhydrogenpolysiloxane, and the like. As component (g), one kind of organohydrogenpolysiloxane may be used, or two or more kinds of organohydrogenpolysiloxanes may be used. Among them, dimethylhydrogensilyl group dimethylpolysiloxane with dimethylhydrogensilyl groups at both ends (dimethylpolysiloxane having a structure of -SiH(CH3)2 at both ends) is suitable as component (g).

[0049] In the composition of the present invention, the value (Gm / Am) of the ratio of the total molar amount (Gm) of the hydrosilyl groups in the component (g) (synonymous with the number of hydrosilyl groups in the component (g)) to the total molar amount (Am) of the alkenyl groups in the component (a) (synonymous with the number of alkenyl groups in the component (a)) is 0.5 to 5.0. By setting the quantitative ratio of the components (a) and (g) in this way, when the composition of the present invention is cured, it is possible to impart an appropriate flexibility while sufficiently forming a three-dimensional network. As a result, for example, even when a large strain is generated in the adhesion part between the gap filler formed by curing the composition of the present invention and a battery cell or a battery module as a base material due to the expansion and contraction of the battery or vibration during running, damage such as cracks, defects, and peeling is less likely to occur in the gap filler. The value (Gm / Am) of the above ratio is more preferably 0.5 to 3.0, and even more preferably 0.8 to 1.4.

[0050] <Component (h-1) silicone resin having an alkenyl group> The composition of the present invention may contain a silicone resin having an alkenyl group as the component (h-1). "Silicone resin" means a silicone having a three-dimensional crosslinked structure. A silicone resin generally has at least one structural unit selected from a monofunctional structural unit (M), a difunctional structural unit (D), a trifunctional structural unit (T), and a tetrafunctional structural unit (Q), and has a three-dimensional crosslinked structure by containing at least one of a trifunctional structural unit (T) and a tetrafunctional structural unit (Q). When the composition of the present invention contains the component (h-1), the component (h-1) preferably contains a silicone resin having a monofunctional structural unit (M) and a tetrafunctional structural unit (Q).

[0051] The silicone resin constituting the component (h-1) preferably contains 0.1 to 10% by mass of an alkenyl group in one molecule, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass. The carbon number of this alkenyl group is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 6, even more preferably 2 to 4, and even more preferably a vinyl group or an allyl group.

[0052] When the composition of the present invention contains the component (h-1), the mechanical strength of the resulting cured product is further enhanced, and a stronger adhesive force can be exhibited. When the composition of the present invention contains the component (h-1), the content of the component (h-1) in the composition is preferably determined in consideration of the content of the component (h-2) as described below.

[0053] The component (h-1) can be dissolved in the component (a) by premixing with the component (a) and heating if necessary. Therefore, it can be incorporated into the composition without increasing the viscosity of the composition of the present invention.

[0054] <Component (h-2) Hydrophobic silica> The composition of the present invention can contain hydrophobic silica as the component (h-2). When the composition of the present invention contains the component (h-2), the mechanical strength of the cured product after the curing reaction can be enhanced, and the adhesive force to the substrate is also further improved.

[0055] The hydrophobic silica constituting the component (h-2) is obtained by treating the surface of silica fine powder such as fumed silica, precipitated silica, or calcined silica with an organopolysilazane compound (preferably an organodisilazane compound such as hexamethyldisilazane), an organosilane compound (such as dimethyldichlorosilane), a diorganopolysiloxane compound (such as dimethylpolysiloxane), etc. to make it hydrophobic.

[0056] The hydrophobic silica constituting the component (h-2) preferably has a volume-based median diameter of 1 to 100 nm, more preferably 5 to 40 nm, in the aggregate of all the particles constituting the component (h-2). Commercially available products can be used as the hydrophobic silica of the component (h-2). For example, AEROSIL 90, 200, 300, R972, R974, or R976 (all manufactured by Evonik) etc. can be mentioned.

[0057] When the composition of the present invention contains component (h-2), its content is preferably determined in consideration of the content of component (h-1). That is, based on 100 parts by mass of the content of component (a), the total content of components (h-1) and (h-2) is preferably 0.1 to 5 parts by mass, may be 0.2 to 4 parts by mass, may be 0.4 to 3 parts by mass, and is also preferably 0.6 to 3 parts by mass. Here, the "total content of components (h-1) and (h-2)" means the content of component (h-1) when the composition of the present invention contains component (h-1) and does not contain component (h-2), means the content of component (h-2) when it does not contain component (h-1) but contains component (h-2), and means the total amount of components (h-1) and (h-2) when it contains both components (h-1) and (h-2).

[0058] <Component (i) Alkenyltrialkoxysilane with an alkenyl group having 3 to 16 carbon atoms> The composition of the present invention can contain an alkenyltrialkoxysilane having an alkenyl group with 3 to 16 carbon atoms as component (i). By the composition of the present invention containing component (i), it becomes possible to further increase the adhesive strength of the composition of the present invention or its cured product.

[0059] The alkenyl group of the alkenyltrialkoxysilane having an alkenyl group with 3 to 16 carbon atoms that constitutes component (i) preferably has 4 to 14 carbon atoms, and more preferably 5 to 12 carbon atoms. This alkenyl group is preferably a linear alkenyl group. The alkoxy group of the alkenyltrialkoxysilane having an alkenyl group with 3 to 16 carbon atoms that constitutes component (i) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, still further preferably 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0060] Preferred specific examples of the alkenyltrialkoxysilane having 3 to 16 carbon atoms that constitutes component (i) include 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, 4-pentenyltrimethoxysilane, 11-dodecenyltrimethoxysilane, and the like.

[0061] Component (i) can form a primary bond or a hydrogen bond with, for example, a hydroxyl group present on the surface of the substrate, and at the same time react with component (g) etc. to act as a crosslinking agent, contributing to the improvement of the adhesive strength.

[0062] When the composition of the present invention contains component (i), the content of component (i) in the composition of the present invention is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the content of component (a). By setting such a content range, the adhesive strength can be further increased while sufficiently ensuring the flexibility of the cured product obtained by curing the composition of the present invention.

[0063] <Other components> The composition of the present invention can contain components other than the above components (a) to (i) as long as the intended effects are not impaired. Examples of such components include compounds having a triple bond between carbon and carbon such as 1-ethynyl-1-cyclohexanol as a curing retardant, colorants such as pigments and dyes, reinforcing agents such as silica and silicone resins containing crosslinkable functional groups by hydrosilylation reaction, adhesion improvers, heat-resistant additives such as metal oxides, antistatic agents, radiation shielding agents, electromagnetic wave shielding agents, preservatives, plasticizers, anti-settling agents, solvents, and the like. When the composition of the present invention contains components other than the above components (a) to (i) (other components), the proportion of the other components other than the solvent in the solid content of the composition (in the case where the composition does not contain a solvent, it means in the composition, and in the case where the composition contains a solvent, it means in all components other than the solvent) is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, preferably 7% by mass or less, preferably 5% by mass or less, and preferably 3% by mass or less.

[0064] [Method for preparing thermally conductive curable silicone composition] The method for preparing the composition of the present invention is not particularly limited as long as the target components are contained in the composition of the present invention. Typically, the composition of the present invention can be obtained by mixing each component to be contained in the composition of the present invention. In the preparation of this composition, when mixing in the coexistence of two or more components having reactive groups with each other, in order to prevent the reaction from proceeding between two or more components having reactive groups with each other, it is preferable to keep the mixing temperature as low as possible and to perform a mixing step for a short time. Further, by storing the prepared composition at a low temperature (for example, 10°C or lower, preferably 5°C or lower) or adding a curing retarder, it is possible to stably store the composition of the present invention without substantially causing the curing reaction.

[0065] In order to more efficiently create the state in which the surface of the heat conductive filler of component (b) is treated with the alkyltrialkoxysilane compound of component (c) as described above, it is also preferable to prepare a mixture of components (b) and (c) in advance and to incorporate this mixture in the preparation of the composition of the present invention. This also applies to the preparation of the following two-component type silicone composition set.

[0066] If the composition of the present invention is prepared immediately before use, an unintended curing reaction before use can be more reliably suppressed. In order to facilitate the preparation of the composition immediately before use, it is also preferable to prepare a two-component silicone composition set (hereinafter also referred to as "the two-component composition set of the present invention") for obtaining the composition of the present invention. Among the constituent components of the composition of the present invention, the "hydrosilylation reaction catalyst" of component (e) is contained only in one of the compositions constituting the two-component composition set, and the "organopolysiloxane compound having 1.5 or more hydrosilyl groups in the molecule and not having an alkenyl group" of component (g) can be contained only in the other composition constituting the two-component composition set. Thereby, regarding the remaining components other than components (e) and (g), whether they are contained only in one of the compositions constituting the two-component composition set, only in the other composition, or in each of the two compositions, the curing reaction hardly occurs in the state of the two-component composition set. In order to more reliably suppress the curing reaction, the two-component composition set of the present invention is preferably stored at a low temperature. There is no particular limitation on how to distribute and contain each component other than components (e) and (g) in the two liquid compositions constituting the two-component composition set of the present invention, and it is sufficient to appropriately set according to the composition of the composition of the present invention prepared by mixing the two liquids. That is, the present invention provides, in one embodiment, the following two-component composition set.

[0067] A two-component composition set for obtaining the composition of the present invention, Composed of a first liquid containing the component (e) and not containing the component (g) and a second liquid containing the component (g) and not containing the component (e), a two-component composition set. In this two-component composition set, all of the essential components constituting the composition of the present invention are contained in the first liquid and / or the second liquid.

[0068] In the two-component composition set of the present invention, as a preferred example of the distribution of each component to the first liquid and the second liquid, the first liquid can contain at least the components (a) to (e), and the second liquid can contain at least the components (a) to (c), (f), and (g).

[0069] According to one embodiment of the present invention, there is provided a method for producing the composition of the present invention, which includes mixing the first liquid and the second liquid of the two-component composition set of the present invention. The method for producing the composition of the present invention preferably includes blending a mixture of the component (b) and the component (c) in the preparation of the first liquid and / or the preparation of the second liquid. In this way, by premixing the component (b) and the component (c) and then blending them, as described above, the component (c) can efficiently interact with the surface of the thermal conductivity filler of the component (b) (for example, undergo a dehydration condensation reaction with the hydroxyl groups on the surface of the thermal conductivity filler), and the surface of the thermal conductivity filler can be modified with higher efficiency.

[0070] By subjecting the composition of the present invention to a curing reaction, a cured product having physical properties suitable as a gap filler for application to batteries mounted on transportation machines or the like can be obtained. That is, even when repeatedly exposed to the expansion and contraction and vibration of the adherend, it is difficult to peel off from the adherend, and it is also difficult to cause damage. A cured product (gap filler) that can continuously exhibit high-efficiency heat dissipation even when repeatedly running in a state installed in a transportation machine (automobile, ship, aircraft, etc.) can be provided. The preferred properties of the cured product that realizes such physical properties will be described, but the present invention is not limited to those having such properties other than those defined in the present invention.

[0071] [Preferred properties of the cured product (gap filler)] <Thermal conductivity> Thermal conductivity is an index indicating the thermal conductivity of the gap filler. For example, considering efficiently transferring the heat generated from the battery cell to the heat sink, the value of the thermal conductivity of the gap filler is preferably 1.5 W / m·K or more, more preferably 2.0 W / m·K or more. This thermal conductivity is usually 1.5 to 10.0 W / m·K, and may also be 2.0 to 5.0 W / m·K. The method for measuring the thermal conductivity is described in the Examples section.

[0072] <Initial maximum shear adhesion strength> The initial maximum shear adhesion strength is an index indicating the initial adhesion strength of the gap filler. For example, considering the expansion and contraction during the initial charge and discharge of an in-vehicle battery cell, and further the adhesion to vibrations during driving, the value of the initial maximum shear adhesion strength of the gap filler is preferably 0.6 MPa or more, more preferably 0.9 MPa or more. There is no particular limitation on the upper limit of the value of the initial maximum shear adhesion strength, and it is usually 2.0 MPa or less. The method for measuring the initial maximum shear adhesion strength is described in the Examples section.

[0073] <Initial maximum shear adhesion strain> The initial maximum shear adhesion strain is an index indicating the flexibility of the gap filler. Considering the expansion and contraction during the initial charge and discharge of an in-vehicle battery cell, and further the adhesion to vibrations during driving, the value of the initial maximum shear adhesion strain of the gap filler is preferably 90% or more, more preferably 140% or more. There is no particular limitation on the upper limit of the value of the initial maximum shear adhesion strain, and it is usually 250% or less. The method for measuring the initial maximum shear adhesion strain is described in the Examples section.

[0074] <Maximum shear adhesion strength after durability test> The maximum shear adhesion strength after the durability test is an index indicating the adhesion strength after continuous vibration and displacement are applied to the gap filler. Considering that the gap filler must maintain adhesion over a long period against the expansion and contraction during repeated charge and discharge cycles applied to in-vehicle battery cells and also against vibrations during driving, it is preferable that the value of the maximum shear adhesion strength of the gap filler after the durability test is 0.5 MPa or more, more preferably 0.7 MPa or more. There is no particular limitation on the upper limit of the value of the maximum shear adhesion strength after the durability test, and it is usually 1.6 MPa or less. The method for measuring the maximum shear adhesion strength after the durability test is described in the Examples section.

[0075] <Maximum shear adhesion strain after the durability test> The maximum shear adhesion strain after the durability test is an index indicating the flexibility after continuous vibration and displacement are applied to the gap filler. Considering that the gap filler must maintain adhesion over a long period against the expansion and contraction during repeated charge and discharge cycles applied to in-vehicle battery cells and also against vibrations during driving, it is preferable that the value of the maximum shear adhesion strain of the gap filler after the durability test is 70% or more, more preferably 120% or more. There is no particular limitation on the upper limit of the value of the maximum shear adhesion strain after the durability test, and it is usually 200% or less. The method for measuring the maximum shear adhesion strain after the durability test is described in the Examples section.

[0076] The curing reaction conditions of the composition of the present invention are not particularly limited as long as the reactive components in the composition of the present invention react sufficiently and the curing reaction proceeds. Therefore, there is no particular limitation on the curing reaction temperature, and for example, it can be 15 to 200°C, preferably 20 to 150°C, and more preferably 20 to 100°C. Also, the pressure during the curing reaction is not particularly limited, and for example, it can be normal pressure (about 0.1 MPa) to 300 MPa, preferably normal pressure to 100 MPa, and more preferably normal pressure to 50 MPa. Also, the reaction time can be appropriately set according to the curing reaction conditions. The composition of the present invention can be sufficiently cured, for example, by a curing reaction of about 10 minutes to 24 hours.

[0077] The present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following Examples except as defined in the present invention.

Examples

[0078] [Example 1] <Preparation of Two - Component Silicone Composition Set>

[0079] - Preparation of the First Liquid - The first liquid having the composition shown in the following table was prepared as follows. A mixture M1 in which component (b) and component (c) were uniformly mixed was obtained. The container of Hibismix 2P - 1 (manufactured by Primix Corporation) was heated to 60°C, component (a) and component (h - 1) were charged, and 2 / 5 of the total amount of mixture M1 was further charged. After mixing and stirring at a rotational speed of 20 rpm for 3 minutes under normal pressure, 1 / 3 of the remaining amount of mixture M1 was charged, and mixing and stirring were carried out for 5 minutes under the same conditions. Then, the temperature was raised so that the material (mixture) temperature reached 100°C, and mixing and stirring were carried out at a rotational speed of 20 rpm for 20 minutes while evacuating. Subsequently, the total amount of the remaining mixture M1 was charged, and mixing and stirring were carried out for 15 minutes under the same conditions. Then, the temperature was raised so that the material temperature reached 140°C, and mixing and stirring were carried out at a rotational speed of 20 rpm for 50 minutes under vacuum. Next, mixing and stirring were carried out for 45 minutes while cooling the temperature so that the material temperature became 80°C or lower. Finally, component (d) and component (e) were added, and mixing and stirring were carried out at a rotational speed of 20 rpm for 30 minutes under vacuum to obtain the "first liquid" in Example 1.

[0080] - Preparation of the Second Liquid - The second liquid having the composition shown in the following table was prepared as follows. A mixture M2 in which component (b) and component (c) were uniformly mixed was obtained. A mixture M2 in which component (b) and component (c) were uniformly mixed was obtained. The container of Hibiscus Mix 2P-1 (manufactured by Primix Corporation) was preheated to 60°C, and component (a) and component (h-1) were added. Then, 2 / 5 of the total amount of mixture M2 was added. After mixing and stirring at a rotation speed of 20 rpm for 3 minutes under normal pressure, 1 / 3 of the remaining mixture M2 was added, and further mixing and stirring were carried out under the same conditions for 5 minutes. Thereafter, the temperature was raised so that the material temperature reached 100°C, and mixing and stirring were carried out at a rotation speed of 20 rpm for 20 minutes while evacuating. Subsequently, the total amount of the remaining mixture M2 was added, and mixing and stirring were carried out under the same conditions for 15 minutes. Then, the temperature was raised so that the material temperature reached 140°C, and mixing and stirring were carried out at a rotation speed of 20 rpm for 50 minutes under vacuum. Next, mixing and stirring were carried out for 45 minutes while cooling the material temperature to 80°C or lower. Finally, component (f), component (g), and component (i) were added, and mixing and stirring were carried out at a rotation speed of 20 rpm for 30 minutes under vacuum to obtain the "Second Liquid" in Example 1.

[0081] <Preparation of Thermally Conductive Curable Silicone Composition> The above-mentioned First Liquid and Second Liquid were filled into a two-component mixing cartridge. A resin static mixer was attached to the tip of the cartridge, and the thermally conductive curable silicone composition in Example 1 was obtained by mixing the First Liquid and the Second Liquid at a volume ratio of 1:1 using a cartridge gun. In this composition, the value of the ratio (Gm / Am) of the total molar amount (Gm) of the hydrosilyl groups in component (g) to the total molar amount (Am) of the alkenyl groups in component (a) was 1.0. This ratio value was the same in other Examples and Comparative Examples.

[0082] <Preparation of Cured Product-1 (Test Piece-1)> The thermally conductive curable silicone composition obtained by mixing the First Liquid and the Second Liquid at a volume ratio of 1:1 using the above-mentioned cartridge gun and static mixer was discharged into a mold with a length of 150 mm, a width of 150 mm, and a thickness of 10 mm. Using a mini test press MP-SCL (manufactured by Toyo Seiki Co., Ltd.), it was pressurized at a pressure of 30 MPa and cured at room temperature (about 25°C) for 24 hours to produce the cured product-1 (test piece-1) in Example 1. This test piece-1 was used for the measurement of thermal conductivity and specific gravity.

[0083] <Preparation of Cured Product-2 (Test Piece-2)> Using the above cartridge gun and static mixer, a thermally conductive curable silicone composition in which the first liquid and the second liquid were mixed at a volume ratio of 1:1 was discharged onto an aluminum (A5052) plate 1 having a length of 60 mm, a width of 25 mm, and a thickness of 2 mm. Onto this discharge surface, an aluminum (A5052) plate 2 having a length of 60 mm, a width of 25 mm, and a thickness of 2 mm, which was separately prepared, was pressed. The long axis directions of the two plates were made to coincide so that the distance between aluminum plates 1 and 2 was 2 mm and the adhesive area between aluminum plates 1 and 2 was 25 mm in the longitudinal direction × 25 mm in the transverse direction, and the two plates were arranged so that an overlap of 25 mm in length occurred. In this state, the cured product-2 (test piece-2) in Example 1 was produced by curing at room temperature (about 25°C) over 24 hours. This test piece-2 has a cured product (gap filler) with a thickness of 2 mm over the entire adhesive area (25 mm × 25 mm) between aluminum plates 1 and 2, and the aluminum plates 1 and 2 are adhered by this cured product. This test piece-2 was used for the measurement of shear adhesive strength and shear adhesive strain.

[0084] [Examples 2 to 35, Comparative Examples 1 to 11] Except that the compositions of the first liquid and the second liquid were as shown in the following table, for each of Examples 2 to 35 and Comparative Examples 1 to 11, in the same manner as in Example 1, a two-component silicone composition set, a thermally conductive curable silicone composition, a cured product-1 (test piece-1), and a cured product-2 (test piece-2) were obtained.

[0085] [Test Examples] <Measurement of Thermal Conductivity> Test piece-1 was used for the measurement of thermal conductivity. Specifically, the thermal conductivity was measured by the hot wire method using a rapid thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Industry Co., Ltd.). <Evaluation Criteria for Thermal Conductivity> ◎: 1.5 W / m·K or more ×: Less than 1.5 W / m·K

[0086] <Measurement of Initial Maximum Shear Adhesion Strength and Maximum Shear Adhesion Strain> Specimen - 2 was attached to an autograph AGX - V (10kN), and in an environment with a temperature of 23°C, it was pulled in the long - axis direction at a speed of 50 mm / min (that is, the aluminum plates 1 and 2 were relatively moved in opposite directions in the long - axis direction) to peel the aluminum plates 1 and 2. Using the maximum load of the load - displacement curve obtained at this time and the value of the displacement corresponding to that point (the relative movement distance in the long - axis direction), the initial maximum shear adhesion strength and the initial maximum shear adhesion strain were obtained from the following formula. Regarding the principle of the measurement method of the maximum shear adhesion strength and the maximum shear adhesion strain, reference can be made to the description in

[0081] and Figure 7 of Japanese Patent Laid - Open No. 2024 - 022613. Also, the "thickness of the cured product (mm)" in the following formula is the thickness before pulling Specimen - 2 in the long - axis direction, that is, 2 mm. {Initial maximum shear adhesion strength (MPa)} = {Maximum load (N)} / {Adhesive area (mm 2 )} {Initial maximum shear adhesion strain (%)} = 100×{Displacement at the point corresponding to the maximum load (mm)} / {Thickness of the cured product (mm)} <Evaluation Criteria for Initial Maximum Shear Adhesion Strength> ◎: 0.9 MPa or more 〇: 0.6 MPa or more and less than 0.9 MPa ×: Less than 0.6 MPa <Evaluation Criteria for Initial Maximum Shear Adhesion Strain> ◎: 140% or more 〇: 90% or more and less than 140% ×: Less than 90%

[0087] <Measurement of Maximum Shear Adhesion Strength and Maximum Shear Adhesion Strain after Durability Test> Specimen - 2 was attached to an autograph AGX - V (10kN), and shear - direction vibrations were applied 2000 times in a strain range of 0 - 1.2 mm at 1 Hz. Then, in the same manner as above, the maximum shear adhesion strength and the maximum shear adhesion strain after the durability test were obtained. <Evaluation Criteria for Maximum Shear Adhesion Strength after Durability Test> ◎: 0.7 MPa or more 〇: 0.5 MPa or more and less than 0.7 MPa ×: Less than 0.5 MPa <Evaluation Criteria for Maximum Shear Adhesion Strain after Durability Test> ◎: 120% or more 〇: 70% or more and less than 120% ×: Less than 70%

[0088] <Measurement of Specific Gravity> A block with a size of 10 mm × 10 mm × 10 mm was cut from Test Piece - 1, and using an automatic specific gravity meter (D - 1: manufactured by Toyo Seiki Co., Ltd.), at a temperature of 23°C, with the density of pure water as 0.998 g / cm 3 the specific gravity of Test Piece - 1 was measured.

[0089] For each of the above Examples and Comparative Examples, the component composition of the composition set or composition and the results of the above respective tests are shown below. In the following table, "propyl", "pentyl", and "octyl" all mean straight chains. Also, "AEROSIL R972" is fumed silica surface - hydrophobized with dimethyldichlorosilane.

[0090]

Table 1 - 1

[0091]

Table 1 - 2

[0092] Examples 1 to 3, Comparative Examples 1 and 2 are experimental examples in which the blending amount of the alkyltrialkoxysilane compound of component (c) is changed. In Examples 1 to 3 (0.5 part by mass, 0.1 part by mass, and 1.5 parts by mass, respectively) where the blending amount of component (c) with respect to 100 parts by mass of the thermally conductive filler of component (b) is in the range of 0.1 to 1.5 parts by mass, all of the obtained cured products were excellent in thermal conductivity and exhibited excellent adhesive strength and adhesive strain (flexibility) both after the initial and durability tests. On the other hand, in Comparative Example 1 where component (c) was not blended, the fluidity of the first liquid or the second liquid was poor in the first place, and test pieces could not be produced. Further, in Comparative Example 2 (1.6 parts by mass) where the blending amount of component (c) with respect to 100 parts by mass of component (b) exceeded 1.5 parts by mass, the obtained cured product was inferior in adhesive strength and flexibility both after the initial and durability tests. When the cured product of Comparative Example 2 was used as a gap filler for a battery cell or a battery module mounted on a transport machine, for example, this gap filler could not sufficiently follow the continuous expansion and contraction of the battery cell or the battery module or the continuous vibration during running, and could not maintain adhesiveness. Comparative Example 3 does not contain the condensation reaction catalyst of component (d) in the composition. The cured product of Comparative Example 3 obtained from this composition was clearly damaged after the durability test and was inferior in practicality as a gap filler or the like.

[0093] [Table 2-1]

[0094] [Table 2-2]

[0095] Comparative Example 4 is an experimental example in which the organosilicon compound of component (f) is not included. Examples 4 to 7 and Comparative Example 5 are experimental examples in which 1,3,5-tris(trimethoxysilylpropyl)isocyanurate (described as "tris(trimethoxysilylpropyl)isocyanurate" in the table) is used as component (f) and the blending amount thereof is changed. The chemical structure of 1,3,5-tris(trimethoxysilylpropyl)isocyanurate is as follows. In the general formula (1), R 1 is all -(CH2) m -Si(OR 3 )3, m and n are both "3", and R 2 and R 3 are both methyl groups.

[0096]

Chemical formula

[0097] The cured product of Comparative Example 4 that does not contain component (f) was inferior in both initial adhesive strength and flexibility, and clearly showed damage after the durability test, and was inferior in practicality as a gap filler or the like. The cured product of Comparative Example 5 in which the content of component (f) was more than that defined in the present invention also had insufficient initial flexibility, and clearly showed damage after the durability test, and was inferior in practicality as a gap filler or the like. On the other hand, the cured products of Examples 4 to 7 containing component (f) in a specific amount defined in the present invention had sufficient adhesiveness and flexibility both initially and after the durability test.

[0098]

Table 3-1

[0099]

Table 3-2

[0100] Examples 8 to 12 and Comparative Example 6 are experimental examples in which 1,3-diallyl-5-trimethoxysilylpropyl isocyanurate is used as component (f) and the blending amount thereof is changed. The chemical structure of 1,3-diallyl-5-trimethoxysilylpropyl isocyanurate is as follows. In the general formula (1), R 1 is an alkenyl group (2-propenyl group (allyl group)) in each case, n is "3", and R 2 is a methyl group.

[0101] [Chemical formula]

[0102] In Comparative Example 6 in which the content of component (f) was more than that specified in the present invention, the initial flexibility of the cured product was insufficient, and furthermore, obvious damage occurred after the durability test, and it was inferior in practicality as a gap filler or the like. On the other hand, the cured products of Examples 8 to 12 containing component (f) in a specific amount specified in the present invention had sufficient adhesiveness and flexibility both initially and after the durability test.

[0103] [Table 4-1]

[0104] [Table 4-2]

[0105] Example 13 is an experimental example in which 1,3,5-tris(trimethoxysilylpentyl) isocyanurate (described as "tris(trimethoxysilylpentyl) isocyanurate" in the table) is used as component (f). The chemical structure of 1,3,5-tris(trimethoxysilylpentyl) isocyanurate is as follows. In the general formula (1), R 1 is each -(CH2) m -Si(OR 3 )3, m and n are both "5", and R 2and R 3 are both methyl groups.

[0106]

Chem.

[0107] Example 14 is an experimental example using 1,3,5-tris(trimethoxysilyloctyl)isocyanurate (described as "tris(trimethoxysilyloctyl)isocyanurate" in the table) as component (f). The chemical structure of 1,3,5-tris(trimethoxysilyloctyl)isocyanurate is as follows. In the general formula (1), R 1 are both -(CH2) m -Si(OR 3 )3, m and n are both "8", and R 2 and R 3 are both methyl groups.

[0108]

Chem.

[0109] Comparative Example 11 is an experimental example using 1,3,5-tris(trimethoxysilylethyl)isocyanurate (described as "tris(trimethoxysilylethyl)isocyanurate" in the table). The component (f) used in Comparative Example 11 is such that in the general formula (1), R 1 are both -(CH2) m -Si(OR 3 )3, m and n are both "2", and R 2 and R 3 are both methyl groups.

[0110] As shown in Table 4-2, in Comparative Example 11 using 1,3,5-tris(trimethoxysilylethyl)isocyanurate in which n in the general formula (1) is 2 (the number of carbon atoms in the alkylene group is shorter than that defined in the present invention) instead of component (f), the cured product was inferior in both adhesiveness and flexibility after the durability test. In contrast, the cured products of Examples 13 and 14 both contain the organosilicon compound of the general formula (1) defined in the present invention as component (f) in the specific amount defined in the present invention. Examples 13 and 14 were excellent in both the adhesive strength and flexibility of the cured product both before and after the durability test. Although not shown in the table, it was also found that when the content of component (f) in Examples 13 and 14 was increased to 12 parts by mass exceeding the upper limit defined in the present invention with respect to 100 parts by mass of component (a), the cured product was damaged after the durability test.

[0111]

Table 5-1

[0112]

Table 5-2

[0113] Comparative Examples 7 to 10 are experimental examples using tetraethoxysilane in place of component (f). Tetraethoxysilane corresponds to the component (C-1) used in the composition described in Japanese Patent No. 7368656. When tetraethoxysilane was used, regardless of its blending amount, the cured product was inferior in both the initial adhesive strength and flexibility. Further, after the durability test, the test pieces were peeled off or broken, and did not satisfy the characteristics of the gap filler required by the present invention. Also, cured products (test pieces - 1 and test pieces - 2) were prepared from the two-component composition (the first liquid and the second liquid) having the composition of Example 1 of Japanese Patent No. 7368656 in the same manner as above and evaluated in the same manner as above. As a result, both the initial adhesive strength and flexibility were inferior (both were rated as ×), and further, after the durability test, the test pieces were peeled off or broken, and did not satisfy the characteristics of the gap filler required by the present invention. It was also found that the specific gravity of the cured product was high.

[0114]

Table 6-1

[0115]

Table 6-2

[0116] Examples 15 to 17 are experimental examples in which the blending amount of component (h-1), which is an optional component, was changed. Examples 15, 18 to 20 are examples in which the blending amount of component (h-2), which is an optional component, was changed. It was found that the cured product exhibited excellent properties as a gap filler whether or not component (h-1) or (h-2) was blended. Although not shown in the table, it was also confirmed that the adhesive strength tended to be further increased by blending a predetermined amount of component (h-1) or (h-2) (the adhesive strength improved in the order of Examples 15, 16, 17, and similarly the adhesive strength improved in the order of Examples 15, 18, 19, 20).

[0117]

Table 7-1

[0118]

Table 7-2

[0119] In Examples 21 to 23, they are experimental examples in which the blending amount of component (i), which is an optional component, was changed. It was found that the cured product exhibited excellent properties as a gap filler whether or not component (i) was blended. Also, a tendency was shown that the adhesive strength was further increased by blending a predetermined amount of component (i).

[0120]

Table 8-1

[0121]

Table 8-2

[0122] Examples 24 to 27 are experimental examples in which the type of the component corresponding to component (i), which is an optional component, is changed. In Example 24, vinyltrimethoxysilane was used; in Example 25, 4-pentenyltrimethoxysilane was used; in Example 26, 11-dodecenyltrimethoxysilane was used; and in Example 27, 17-octadecenyltrimethoxysilane was used. It was found that the alkenyltrialkoxysilane of component (i) contributes to higher adhesive strength and flexibility because the number of carbon atoms in the alkenyl group is in the range of 3 to 16. Conversely, it was also found that when an alkenyltrialkoxysilane having the number of carbon atoms in the alkenyl group outside the range of 3 to 16 is blended, the flexibility tends to decrease more than when not blended (comparison between Example 23 and Examples 24 and 27).

[0123]

Table 9-1

[0124]

Table 9-2

[0125] Examples 28 to 31 are examples in which the blending amount of the thermally conductive filler (aluminum hydroxide) of component (b) is changed. It was found that the cured product exhibits excellent properties as a gap filler regardless of the blending amount of component (b). Further, it was also found that by setting the blending amount of component (b) in the composition to 67 to 73% by volume, both the adhesive strength and flexibility of the cured product can be achieved at a higher level.

[0126]

Table 10-1

[0127]

Table 10-2

[0128] Examples 32 to 34 are experimental examples in which the blending amount of component (b) (aluminum oxide) is changed. Example 35 is an example in which aluminum hydroxide and aluminum oxide are used in combination as component (b). It can be seen that by using aluminum hydroxide as component (b), the specific gravity of the cured product can be suppressed.

[0129] As described above, by setting the composition of the composition of the present invention, the cured product obtained by curing this composition can have excellent adhesive strength and flexibility, and further, these properties can be stably maintained even when exposed to repeated vibration stress. It was also shown that it can be done. Therefore, the composition of the present invention can be suitably used, for example, for forming a gap filler used for a battery mounted on a transportation machine.

Claims

1. A thermally conductive curable silicone composition, wherein the thermally conductive curable silicone composition contains the following components (a) to (g): (a) A linear organopolysiloxane compound having 1.5 to 2.0 alkenyl groups at the molecular chain terminals and no hydrosilyl group; (b) A thermally conductive filler; (c) An alkyltrialkoxysilane compound; (d) A condensation reaction catalyst; (e) A hydrosilylation reaction catalyst; (f) An organosilicon compound represented by the following general formula (1); 【Chemical 1】 In the formula, R １ each independently represents an alkenyl group or -(CH ２ ) ｍ -Si(OR ３ ) ３ . R ２ and R ３ each independently represent an alkyl group having 1 to 4 carbon atoms. n is an integer from 3 to 8, and m is an integer from 0 to 8. (g) An organopolysiloxane compound having 1.5 or more hydrosilyl groups in the molecule and no alkenyl group; the content of the component (f) is 0.5 to 10 parts by mass with respect to 100 parts by mass of the content of the component (a), in the thermally conductive curable silicone composition, the content of the component (b) is 60 to 82% by volume, the content of the component (c) is 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the content of the component (b), the value (Gm / Am) of the ratio of the total molar amount (Gm) of the hydrosilyl groups in the component (g) to the total molar amount (Am) of the alkenyl groups in the component (a) is 0.5 to 5.0, A thermally conductive curable silicone composition.

2. the thermally conductive curable silicone composition contains at least one of the following components (h-1) and (h-2): (h-1) A silicone resin having an alkenyl group; (h-2) Hydrophobic silica; the total content of the components (h-1) and (h-2) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the content of the component (a), The thermally conductive curable silicone composition according to claim 1.

3. the thermally conductive curable silicone composition contains the following component (i): (i) An alkenyltrialkoxysilane having 3 to 16 carbon atoms in the alkenyl group; the content of the component (i) is 0.1 to 3 parts by mass with respect to 100 parts by mass of the content of the component (a), The thermally conductive curable silicone composition according to claim 2.

4. the component (b) contains at least one of aluminum hydroxide and aluminum oxide, and the content of the component (b) in the thermally conductive curable silicone composition is 67 to 73% by volume, The thermally conductive curable silicone composition according to claim 3.

5. the proportion of the aluminum hydroxide in the component (b) is 70% by volume or more, The thermally conductive curable silicone composition according to claim 4.

6. A cured product obtained by curing the thermally conductive curable silicone composition according to any one of claims 1 to 5.

7. A gap filler comprising the cured product according to claim 6.

8. The gap filler according to claim 7, for application to a battery mounted on a transport machine.

9. A two-component silicone composition set for obtaining the thermally conductive curable silicone composition according to any one of claims 1 to 5, which is composed of a first liquid containing the component (e) and not containing the component (g) and a second liquid containing the component (g) and not containing the component (e).

10. The two-component silicone composition set according to claim 9, wherein the first liquid contains at least the components (a) to (e), and the second liquid contains at least the components (a) to (c), (f), and (g).

11. A method for producing the thermally conductive curable silicone composition according to any one of claims 1 to 5, comprising mixing the first liquid and the second liquid of the two-component silicone composition set according to claim 9.

12. The method for producing the thermally conductive curable silicone composition according to claim 11, comprising blending a mixture of the component (b) and the component (c) in the preparation of the first liquid and / or the preparation of the second liquid.

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