Thermally conductive composition, thermally conductive member, and battery assembly

Abstract

This thermally conductive composition comprises an organic polymer having a hydrolyzable silyl group, a plasticizer, an amino group-containing alkoxysilane or a partial condensate thereof, and a thermally conductive filling material, wherein the concentration of an alkoxy group of the amino group-containing alkoxysilane is at most 0.00035 mol / cm3 with respect to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the amino group-containing alkoxysilane or partial condensate thereof.

Description

Thermally conductive composition, thermally conductive member, and battery assembly

[0001] The present invention relates to a thermally conductive composition, a thermally conductive member made from a cured product of the composition, and a battery assembly including the member.

[0002] Thermally conductive resin compositions are widely known in curable liquid form. For example, they are used as thermally conductive materials, such as heat-dissipating gap fillers, which are filled between a heat-generating element and a heat-dissipating element and then cured to form a cured product that transfers heat generated by the heat-generating element to the heat-dissipating element. In recent years, with the steady growth in the production volume of electric vehicles, there has been an increasing demand for two-component, room-temperature curing thermally conductive resin compositions for lithium-ion batteries (LiBs). Specifically, in lithium-ion batteries, from the perspective of heat dissipation, thermally conductive resin compositions are often filled between components such as battery cells, battery modules, and battery packs to secure the components and improve heat dissipation. Several technologies related to such thermally conductive compositions have been reported.

[0003] For example, Patent Document 1 discloses an invention relating to a curable composition based on an organic polymer containing a reactive silane group, which exhibits a high thermal conductivity of at least 2 W / m·K according to ASTM D5470 and is suitable as a gap filler, sealant, or adhesive for batteries and electronic devices. Patent Document 2 discloses an invention relating to a composition having high workability, fast curing, and thermal conductivity, which contains a filler component having an average particle size within a certain range, a polyalkylene glycol having a hydrolyzable silyl group, a curing catalyst, and a silane coupling agent. Patent Document 3 discloses an invention relating to a curable adhesive composition for batteries that has moderate adhesive strength and good reworkability, which contains an organic polymer having a hydrolyzable silyl group and a thermally conductive filler, and has a Shore A hardness and shear strength within a certain range after curing.

[0004] JP 2022-520317 A, Patent Publication No. 5828835, International Publication No. 2023 / 190722

[0005] Thermally conductive members formed by curing conventional thermally conductive compositions are used, for example, between adherends such as heat-generating bodies and heat-dissipating bodies as described above, but in actual use environments, exposure to high temperatures during charging and discharging can cause the cured product to harden and elongate less, resulting in problems such as being unable to follow the cell expansion during rapid charging and peeling off, making it impossible for the thermally conductive member to fulfill its intended role of fixing components together or enhancing heat dissipation.

[0006] Therefore, an object of the present invention is to provide a thermally conductive composition that has excellent elongation when cured before heating, and that prevents a decrease in elongation even when the cured product is exposed to a high-temperature environment of, for example, 80°C for a long period of time.

[0007] As a result of extensive investigation, the present inventors have found that the above-mentioned problems can be solved by adjusting the alkoxy group concentration or the mz59 / total peak intensity to a certain level or less in a thermally conductive composition containing an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler. That is, the present invention provides the following [1] to

[18] .

[0008] [1] A thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler, wherein the concentration of the alkoxy group of the alkoxysilane having an amino group relative to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof is 0.00035 mol / cm ３[2] A thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler, wherein the surface of a cured product of the thermally conductive composition has a peak intensity of mz59 / total of 0.120 or less when measured by TOF-SIMS. [3] The thermally conductive composition according to [1] or [2], which comprises an alkoxysilane having an amino group. [4] The thermally conductive composition according to [1], which is composed of a combination of a first part containing the plasticizer, the alkoxysilane having an amino group or a partial condensate thereof, and the thermally conductive filler, which is filled in a first container but does not contain the organic polymer having a hydrolyzable silyl group, and a second part containing the organic polymer having a hydrolyzable silyl group, the plasticizer, the thermally conductive filler, and water, which is filled in a second container but does not contain the alkoxysilane having an amino group or a partial condensate thereof. [5] The thermally conductive composition according to any one of [1] to [4], wherein the organic polymer having a hydrolyzable silyl group is linear. [6] The thermally conductive composition according to any one of [1] to [5], wherein the organic polymer having a hydrolyzable silyl group has a number-average molecular weight of 1,000 or more. [7] The thermally conductive composition according to any one of [1] to [6], wherein the content of the thermally conductive filler is 65 volume % or less based on the total volume of the thermally conductive composition. [8] The thermally conductive composition according to any one of [1] to [7], wherein the thermally conductive filler comprises aluminum hydroxide. [9] The thermally conductive composition according to any one of [1] to [8], wherein the thermally conductive filler comprises aluminum oxide.

[10] The thermally conductive composition according to any one of [1] to [9], wherein the thermal conductivity of a cured product of the thermally conductive composition is 1.0 W / m K or more.

[11] The thermally conductive composition according to any one of [1] to

[10] , wherein the alkoxysilane having an amino group or a partial condensate thereof has three or more alkoxy groups in one molecule.

[12] The concentration of the alkoxy groups is 0.00003 mol / cm ３

[13] The thermally conductive composition according to any one of [1] to

[12] , wherein the peak intensity of mz59 / total obtained by measuring the surface of a cured product of the thermally conductive composition by TOF-SIMS is 0.030 or more.

[14] The thermally conductive composition according to any one of [1] to

[13] , wherein the peak intensity of mz59 / total obtained by measuring the surface of a cured product of the thermally conductive composition by TOF-SIMS is 0.120 or less.

[15] The thermally conductive composition according to any one of [1] to

[13] , wherein the concentration of the alkoxy group of the alkoxysilane having an amino group relative to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof is 0.00035 mol / cm ３

[16] A thermally conductive member comprising a cured product of the thermally conductive composition according to any one of [1] to

[15] .

[17] A battery assembly comprising the thermally conductive member according to

[16] .

[18] Use of the thermally conductive member according to

[16] as a heat dissipation material for a battery assembly.

[0009] According to the present invention, it is possible to provide a thermally conductive composition in which the cured product before heating has excellent elongation, and in which the reduction in elongation is suppressed even when the cured product is exposed to a high-temperature environment of, for example, 80°C for a long period of time.

[0010] 1 is a schematic diagram showing a container set according to an embodiment; FIG. 2 is a schematic diagram showing a container set according to an embodiment; FIG. 3 is a perspective view showing a typical configuration of a battery module; FIG. 4 is a perspective view showing a typical configuration of a battery cell; FIG. 5 is a perspective view showing a battery assembly having a cell-to-pack structure;

[0011] [Thermal Conductive Composition] The thermal conductive composition of the present invention will be described below with reference to first and second embodiments. (First Embodiment) A thermal conductive composition according to one embodiment of the present invention (hereinafter also referred to as the first embodiment) comprises an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler. The composition has a concentration of alkoxy groups in the alkoxysilane having an amino group (hereinafter also referred to as the "alkoxy group concentration") relative to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof ... and a thermally conductive filler. ３ The alkoxy group concentration is 0.00035 mol / cm or less. ３ When the alkoxy group concentration is 0.00032 mol / cm or less, reduction in elongation can be sufficiently suppressed even when the thermally conductive member described below is exposed to a high-temperature environment for a long period of time. ３ It is preferable that the concentration is 0.00030 mol / cm or less. ３ More preferably, it is:

[0012] The reason why a thermally conductive member (described later) can sufficiently suppress a decrease in elongation when exposed to a high-temperature environment for a long period of time when the alkoxy group concentration is below a certain level is unclear, but is presumed to be as follows. Generally, alkoxysilanes having amino groups and their partial condensates have a higher proportion of alkoxy groups in their molecular weight compared to organic polymers having hydrolyzable silyl groups. Furthermore, preferred alkoxysilanes having amino groups and their partial condensates have multiple alkoxy groups, such as trialkoxysilyl groups and dialkoxysilyl groups. Such alkoxy groups are most reactive in the first reaction, while the second and third alkoxy groups become less reactive due to steric hindrance and reduced mobility within the material. Therefore, during the initial curing of the thermally conductive composition, the first and second alkoxy groups react and are easily incorporated into a crosslinked structure, but some of the second alkoxy groups and the third alkoxy group may easily remain unreacted. Therefore, when a cured product of the thermally conductive composition is obtained and the cured product is exposed to a high-temperature environment for a long period of time, the remaining alkoxy groups derived from the alkoxysilane having an amino group and its partial condensate gradually react to form a new crosslinked structure, which is thought to reduce the elongation of the cured product. Therefore, when the alkoxy group concentration is below a certain level, the amount of unreacted groups decreases, and the elongation is thought to be reduced.

[0013] The alkoxy group concentration is 0.00003 mol / cm ３ It is preferable that the concentration is 0.00005 mol / cm or more. ３ More preferably, it is 0.0001 mol / cm or more. ３It is even more preferable that the alkoxy group concentration is equal to or higher than this. As the alkoxy group concentration increases, it becomes easier to impart excellent adhesive strength to the cured product of the thermally conductive composition, and interfacial peeling becomes less likely to occur. The alkoxy group concentration can be adjusted to a desired range by adjusting the type and blending of the alkoxysilane having an amino group or its partial condensate, and the organic polymer having a hydrolyzable silyl group, which will be described later. The alkoxy group concentration can be calculated from the structure and blending of the alkoxysilane having an amino group or its partial condensate, and a detailed calculation method is as described in the Examples below.

[0014] <Alkoxysilane Having an Amino Group and a Partial Condensate Thereof> The thermally conductive composition according to the first embodiment of the present invention contains an alkoxysilane having an amino group or a partial condensate thereof. By including an alkoxysilane having an amino group or a partial condensate thereof, the adhesive strength of the thermally conductive composition can be increased by the amino group, and the curability of the thermally conductive composition can be increased by the alkoxy group, thereby achieving both adhesiveness and curability. The inclusion of an alkoxysilane having an amino group makes it easier to maintain the elongation of the cured product at a certain level or higher before heating. Furthermore, since the partial condensate of an alkoxysilane having an amino group generates few additional reactions after the cured product is formed, the inclusion of the partial condensate makes it easier to suppress a decrease in elongation even when the cured product is exposed to a high-temperature environment. The thermally conductive composition according to the first embodiment of the present invention may contain either an alkoxysilane having an amino group or a partial condensate thereof, but preferably contains an alkoxysilane having an amino group. The use of an alkoxysilane having an amino group makes it easier to improve the elongation of the cured product before heating. Furthermore, the use of a partial condensate makes it easier to further suppress a decrease in elongation even when the cured product is exposed to a high-temperature environment for a long period of time.

[0015] Specific examples of alkoxysilanes having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, [3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine, N-(n-butyl)-3-aminopropyltrimethoxysilane, N-(n-butyl)-3-aminopropyltriethoxysilane, bis(3-trimethoxysilylpropyl)amine, bis(3-triethoxysilylpropyl)amine, trimethoxysilylpropyldiethylenetriamine, and triethoxysilylpropyldiethylenetriamine.

[0016] From the viewpoint of easily improving the adhesive strength and curing properties of the thermally conductive composition, the alkoxysilane having an amino group preferably has three or more alkoxy groups in one molecule, and more preferably has a structure in which three alkoxy groups are bonded to one silicon atom. Furthermore, from the viewpoint of improving adhesive strength, the alkoxysilane having an amino group preferably has at least one of a primary amino group or a secondary amino group, and more preferably has a primary amino group. Alkoxysilanes having both a primary amino group and a secondary amino group are also preferred. Among the above-mentioned alkoxysilanes having an amino group, those having a 2-aminoethyl group, such as N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, and N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, are preferred, and NH ２ CH ２ CH２ More preferred are those having a (2-aminoethyl)-3-amino skeleton, which is an NH- structure, and among these, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is even more preferred.

[0017] Examples of the partial condensate of alkoxysilane having an amino group include an alkoxysilane oligomer which is a hydrolysis condensate of an aminoalkoxysilane and an alkylalkoxysilane, and an alkoxysilane oligomer which is a hydrolysis condensate of an aminoalkoxysilane. Among these, an alkoxysilane oligomer which is a hydrolysis condensate of an aminoalkoxysilane and an alkylalkoxysilane is preferred. The partial condensate of alkoxysilane having an amino group is also preferably one having three or more alkoxy groups in one molecule.

[0018] The aminoalkoxysilane constituting the alkoxysilane oligomer is similar to the alkoxysilane having an amino group described above as a monomer, and therefore a detailed description thereof will be omitted. Examples of alkylalkoxysilanes constituting the alkoxysilane oligomer include monoalkyltrialkoxysilanes in which one alkyl group and three alkoxy groups are directly bonded to the silicon atom, and dialkyldialkoxysilanes in which two alkyl groups and two alkoxy groups are directly bonded to the silicon atom. Specific examples of monoalkyltrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, etc. Specific examples of dialkyldialkoxysilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, etc. Among these, monoalkyltrialkoxysilanes are preferred, and ethyltriethoxysilane is more preferred. The amino group is bonded to a portion of the alkyl group.

[0019] The alkoxysilane having an amino group and the partial condensate thereof may both be commercially available products, and for example, a commercially available product of the alkoxysilane having an amino group such as "KBM-603" manufactured by Shin-Etsu Silicones Co., Ltd. Furthermore, a commercially available product of the partial condensate of the alkoxysilane having an amino group such as "Dynasylane 1146" manufactured by Evonik and "VX225" manufactured by Momentive Corporation can be used.

[0020] The content of the alkoxysilane having an amino group or a partial condensate thereof is not particularly limited as long as the alkoxy group concentration can be adjusted to a certain level or less, but is preferably 7 parts by mass or less per 100 parts by mass of the total amount of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof. It is more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. The content of the alkoxysilane having an amino group or a partial condensate thereof is not particularly limited, but is preferably 0.1 parts by mass or more per 100 parts by mass of the total amount of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof. It is more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more.

[0021] <Organic Polymer Having Hydrolyzable Silyl Groups> The thermally conductive composition according to the first embodiment of the present invention includes an organic polymer having hydrolyzable silyl groups. The hydrolyzable silyl groups contained in the organic polymer are hydrolyzed by moisture such as humidity to form silanol groups, which can then undergo condensation polymerization to form siloxane bonds between the silanol groups or between the silanol groups and the hydrolyzable silyl groups. This allows the organic polymer to form a crosslinked structure and harden, resulting in a rubber-like elastomer. Note that the silanol group refers to a hydroxy group (Si—OH) directly bonded to a silicon atom.

[0022] A hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. The hydrolyzable groups of the hydrolyzable silyl group are not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, an alkoxysilyl group is preferred as the hydrolyzable silyl group because of its mild hydrolysis reaction. Examples of the alkoxysilyl group include trialkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, and a triphenoxysilyl group; dialkoxysilyl groups such as a dimethoxymethylsilyl group and a diethoxymethylsilyl group; and monoalkoxysilyl groups such as a methoxydimethylsilyl group and an ethoxydimethylsilyl group. Among these, from the viewpoint of appropriately forming three-dimensional crosslinks when the thermally conductive composition is cured and easily suppressing a decrease in elongation in a high-temperature environment, dialkoxysilyl groups are more preferred, and dimethoxymethylsilyl groups are particularly preferred.

[0023] The organic polymer having a hydrolyzable silyl group may be linear or branched, but is preferably linear. Incidentally, as typified by polypropylene oxide, a polymer having an alkyl group with approximately 1 or 2 carbon atoms in its side chain, such as a methyl group, is also considered linear. That is, the organic polymer having a hydrolyzable silyl group of the present invention preferably has a hydrolyzable silyl group at the end of a linear molecular chain. Having a linear molecular chain makes it easier to adjust the elongation of the cured product before heating to a certain level or higher. The thermally conductive composition according to the first embodiment of the present invention may contain both an organic polymer having a linear hydrolyzable silyl group and an organic polymer having a branched hydrolyzable silyl group. However, from the perspective of the elongation of the cured product before heating, the content of the organic polymer having a branched hydrolyzable silyl group should be low from the perspective of the elongation of the cured product before heating. Specifically, the content is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the organic polymer having a hydrolyzable silyl group, and may be 0% by mass or more.

[0024] The terminal silylation rate of the organic polymer having a hydrolyzable silyl group is preferably 50% or more, more preferably 60% or more, and even more preferably 65% ​​or more. When the terminal silylation rate is a certain level or more, it becomes easier to appropriately adjust the curability and elongation of the thermally conductive composition. The terminal silylation rate means the ratio of silylated terminals to all terminals of the organic polymer having a hydrolyzable silyl group. There is no particular upper limit to the terminal silylation rate, but it is, for example, 100% or less, and in practical use, can be 99% or less. The terminal silylation rate of the organic polymer having a hydrolyzable silyl group is １ It is determined by H-NMR.

[0025] The average number of hydrolyzable silyl groups in one molecule of the organic polymer having hydrolyzable silyl groups is preferably 1 to 3. When the number of hydrolyzable silyl groups in the polymer is within this range, the thermally conductive composition has good curability and elongation. The average number of hydrolyzable silyl groups in one molecule of the organic polymer having hydrolyzable silyl groups can be measured by the following method: １ It can be calculated based on the concentration of hydrolyzable silyl groups in the organic polymer determined by H-NMR and the number average molecular weight of the polymer determined by GPC.

[0026] The method for introducing a hydrolyzable silyl group into an organic polymer is not particularly limited, and examples thereof include (1) a method in which an organic polymer modified with an unsaturated group in the molecule is subjected to hydrosilylation by the action of a hydrosilane having a hydrolyzable silyl group, (2) a method in which an organic polymer modified with an unsaturated group in the molecule is reacted with a compound having a mercapto group and a hydrolyzable silyl group, and (3) a method in which an organic polymer having a functional group in the molecule is reacted with a compound having a hydrolyzable silyl group and a functional group reactive with the functional group.Specific examples of the reaction that can be used include a reaction between an isocyanate group and a hydroxyl group, a reaction between an isocyanate group and an amino group, and a reaction between an isocyanate group and a mercapto group.

[0027] The organic polymer containing a hydrolyzable silyl group is not particularly limited, and examples thereof include polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymers, and polypropylene oxide-polybutylene oxide copolymers; saturated hydrocarbon polymers; polychloroprene, polyisoprene, copolymers of isoprene or butadiene with acrylonitrile and / or styrene; polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene; (meth)acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth)acrylate and butyl (meth)acrylate; Examples of such polymers include vinyl polymers obtained by radical polymerization of monomers such as vinyl acid, acrylonitrile, and styrene, graft polymers obtained by polymerizing vinyl monomers into the above polymers, polysulfide polymers, nylon 6 obtained by ring-opening polymerization of ε-caprolactam, nylon 6,6 obtained by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6,10 obtained by condensation polymerization of hexamethylenediamine and sebacic acid, nylon 11 obtained by condensation polymerization of ε-aminoundecanoic acid, nylon 12 obtained by ring-opening polymerization of ε-aminolaurolactam, polyamide polymers such as copolymer nylons containing two or more of the above nylon components, polycarbonate polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, and diallyl phthalate polymers. In this specification, (meth)acrylate means methacrylate or acrylate.

[0028] Among these, polyalkylene oxides are preferred as organic polymers from the viewpoint of improving adhesive strength and elongation after curing. That is, as organic polymers having hydrolyzable silyl groups, polyalkylene oxides having hydrolyzable silyl groups are preferred. Among polyalkylene oxides, polypropylene oxide is particularly preferred. The organic polymers containing hydrolyzable silyl groups may be used alone or in combination of two or more.

[0029] The number average molecular weight (Mn) of the organic polymer containing hydrolyzable silyl groups is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. When the number average molecular weight of the organic polymer containing hydrolyzable silyl groups is above these lower limits, it is easy to adjust the elongation of the cured product to a certain level or higher. Furthermore, the number average molecular weight (Mn) of the organic polymer containing hydrolyzable silyl groups is preferably 70,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. When the number average molecular weight of the organic polymer containing hydrolyzable silyl groups is below these upper limits, the viscosity of the resulting thermally conductive composition is reduced, improving coatability. Note that when the thermally conductive composition contains multiple types of organic polymers containing hydrolyzable silyl groups, the number average molecular weight (Mn) refers to the number average molecular weight (Mn) of all of them.

[0030] In the present invention, the number average molecular weight of the organic polymer containing a hydrolyzable silyl group refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene. Measurement by GPC can be performed, for example, using an ACQUITY APC system manufactured by Waters Corporation, a Shodex KF604 GPC column manufactured by Tosoh Corporation, tetrahydrofuran as the solvent, a column temperature of 40° C., and a flow rate of 0.3 ml / min.

[0031] The polymer containing a hydrolyzable silyl group can be a commercially available product. For example, examples of polyalkylene oxide polymers having a polypropylene oxide main chain skeleton and a dimethoxysilyl group at the end of the main chain skeleton include those manufactured by Asahi Glass Co., Ltd. under the product names "Excestar A2410" and "Excestar S4530," and those manufactured by Kaneka Corporation under the product names "S203," "S327," "SAT350," "SAX010," and "SAX220."

[0032] <Thermal conductive filler> The thermal conductive composition according to the first embodiment of the present invention contains a thermal conductive filler. By including the thermal conductive filler, the thermal conductivity of the thermal conductive composition is improved. In the case of a two-component curing type, the thermal conductive filler may be included in at least one of the first part and the second part, but it is preferable that the thermal conductive filler be included in both the first part and the second part.

[0033] Examples of thermally conductive fillers include metals, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides, nitrides, and carbides other than metals. The thermally conductive filler may be spherical or in the form of an irregular powder. Examples of metals in the thermally conductive filler include aluminum, copper, and nickel. Examples of metal oxides include aluminum oxide (e.g., alumina), magnesium oxide, and zinc oxide. Examples of metal nitrides include aluminum nitride. Examples of metal hydroxides include aluminum hydroxide. Examples of carbon materials include spherical graphite. Examples of oxides, nitrides, and carbides other than metals include quartz, boron nitride, and silicon carbide. Among these, from the viewpoint of ensuring insulation, metal oxides, metal nitrides, metal hydroxides, carbon materials, oxides, nitrides, and carbides other than metals are preferred, with metal oxides and metal hydroxides being more preferred. Among the above, aluminum oxide is preferred from the viewpoint of improving the heat dissipation properties of the thermally conductive composition, and aluminum hydroxide is preferred when it is desired to improve flame retardancy or when it is desired to reduce the specific gravity of the inorganic filler to make the thermally conductive composition lighter. Furthermore, in order to achieve high thermal conductivity while keeping the specific gravity of the thermally conductive composition low and reducing its weight, it is also preferable to use aluminum oxide and aluminum hydroxide in combination. When these are used in combination, the ratio (volume ratio) of the filling rate of aluminum hydroxide to the filling rate of aluminum oxide is preferably 0.1 or more and 30 or less, more preferably 0.2 or more and 15 or less, and even more preferably 0.3 or more and 10 or less. The thermally conductive fillers described above may be used alone or in combination of two or more.

[0034] The average particle size of the thermally conductive filler is preferably 0.1 μm or more and 200 μm or less, more preferably 0.5 μm or more and 150 μm or less, and even more preferably 1 μm or more and 110 μm or less. It is preferable to use a small-particle thermally conductive filler with an average particle size of 0.1 μm or more and 5 μm or less in combination with a large-particle thermally conductive filler with an average particle size of more than 5 μm and 200 μm or less. The small-particle thermally conductive filler preferably has an average particle size of 0.3 μm or more and 4 μm or less, and the large-particle thermally conductive filler more preferably has an average particle size of 8 μm or more and 150 μm or less. The filling rate can be increased by using thermally conductive fillers with different average particle sizes. The average particle size of the thermally conductive filler can be measured by observation using an electron microscope or the like. More specifically, the particle sizes of 50 random thermally conductive fillers can be measured using, for example, an electron microscope or optical microscope, and the average (arithmetic mean) of the measurements can be used as the average particle size.

[0035] The content (filling rate) of the thermally conductive filler in the thermally conductive composition is preferably 70% by volume or less, more preferably 65% ​​by volume or less, and even more preferably 62% by volume or less, relative to the total volume of the thermally conductive composition. When the content of the thermally conductive filler is equal to or less than the above upper limit, the elongation of the cured product before heating is easily increased. Furthermore, the content of the thermally conductive filler in the thermally conductive composition is preferably 45% by volume or more, more preferably 50% by volume or more, and even more preferably 55% by volume or more, relative to the total volume of the thermally conductive composition. When the content of the thermally conductive filler is equal to or more than the above lower limit, a certain level of thermal conductivity can be imparted to the thermally conductive composition.

[0036] <Plasticizer> The thermally conductive composition according to the first embodiment of the present invention contains a plasticizer. By including a plasticizer in the thermally conductive composition, the flexibility and elongation of the cured product can be increased. In addition, the viscosity is likely to be reduced, improving workability and the like.

[0037] Specific examples of plasticizers include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, organic phosphorus-based plasticizers such as organic phosphate plasticizers and organic phosphite plasticizers, and epoxy-based plasticizers such as sulfonamides and epoxidized soybean oil. Furthermore, the plasticizer is preferably an organic ester plasticizer. Examples of the monobasic organic acid ester include glycol esters obtained by reacting glycol with a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, n-nonylic acid, decylic acid, and benzoic acid.

[0038] Examples of the polybasic organic acid ester include ester compounds of a polybasic organic acid with an alcohol having a linear or branched structure and having 3 to 10 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, azelaic acid, and 1,2-cyclohexanedicarboxylic acid. Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol Examples of suitable organic ester plasticizers include di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, diisononyl 1,2-cyclohexanedicarboxylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified alkyd sebacate, and a mixture of a phosphate ester and an adipate. Organic ester plasticizers other than those listed above may also be used. Adipic acid esters other than those listed above may also be used.

[0039] Examples of the organic phosphorus plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate. The plasticizer is preferably a diester plasticizer represented by the following formula (1) or (2):

[0040] In the above formula (1), R1 and R2 each represent an organic group having 2 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group, or an n-propylene group, and p represents an integer of 3 to 10. In the above formula (1), R1 and R2 each preferably represent an organic group having 5 to 10 carbon atoms, and more preferably represent an organic group having 6 to 10 carbon atoms.

[0041] In the above formula (2), R4 and R5 each represent a hydrocarbon group having 3 to 10 carbon atoms, and R6 represents a hydrocarbon group having 2 to 10 carbon atoms. In the above formula (2), R4 and R5 each preferably have 4 to 9 carbon atoms, and more preferably have 6 to 9 carbon atoms. The hydrocarbon groups of R4 and R5 are preferably alkyl groups. The alkyl group may be linear or may have a branched structure. R6 preferably has 4 to 9 carbon atoms, and more preferably has 5 to 8 carbon atoms. The hydrocarbon group of R6 is preferably an aliphatic hydrocarbon group, and of these, an unsaturated aliphatic hydrocarbon group is more preferred. R6 may be linear or may have a branched or cyclic structure, and preferably has a cyclic structure. One type of plasticizer may be used alone, or two or more types may be used in combination.

[0042] The plasticizer preferably includes triethylene glycol di-2-ethylhexanoate (3GO), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), diisononyl adipate (DINA), triethylene glycol di-2-ethylbutyrate (3GH), or triethylene glycol di-2-ethylpropanoate. The plasticizer preferably includes diisononyl adipate (DINA), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), or triethylene glycol di-2-ethylhexanoate (3GO), and particularly preferably includes diisononyl 1,2-cyclohexanedicarboxylate (DINCH).

[0043] From the viewpoint of reducing the viscosity of the composition, the molecular weight of the plasticizer is preferably less than 1,000, more preferably less than 500, and preferably 50 or more, more preferably 100 or more. Furthermore, the molecular weight of the plasticizer is preferably 50 or more and less than 1,000, more preferably 100 or more and less than 500. When the structural formula of the plasticizer is known, the molecular weight is a molecular weight calculated from the structural formula. When the structural formula is unknown, the molecular weight can be measured using a mass spectrometer (GC-MS or LC-MS).

[0044] The content of the plasticizer in the thermally conductive composition is preferably 30 to 300 parts by mass, more preferably 50 to 200 parts by mass, and even more preferably 80 to 180 parts by mass, per 100 parts by mass of the organic polymer having a hydrolyzable silyl group. When the amount of plasticizer is above these lower limits, the viscosity of the composition decreases, improving workability. When the amount of plasticizer is below these upper limits, the amount of binder can be kept above a certain level, ensuring a certain number of reaction sites with the thermally conductive filler, and making it easier to improve thermal conductivity.

[0045] <Water> The thermally conductive composition according to the first embodiment of the present invention may contain water. By containing water, for example, it is possible to add a catalyst as needed, as described below, or to cure the thermally conductive composition by mixing the first and second parts described below. The content of water is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the organic polymer having a hydrolyzable silyl group.

[0046] <Dehydrating Agent> The thermally conductive composition according to the first embodiment of the present invention may contain a dehydrating agent. By including the dehydrating agent, it is possible to prevent the thermally conductive composition from being hardened by moisture contained in the air or the like during storage of the thermally conductive composition.

[0047] The dehydrating agent is preferably used in the case of a two-component curing type described below, and may be contained in either the first or second part, but it is preferable to contain it in the first part but not in the second part, which allows the first part to contain the dehydrating agent and the second part to contain water.

[0048] Examples of dehydrating agents include vinylsilane compounds such as vinyltrimethoxysilane, and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination of two or more. Among these, vinylsilane compounds such as vinyltrimethoxysilane are preferred.

[0049] The content of the dehydrating agent in the thermally conductive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the organic polymer having a hydrolyzable silyl group. When the content of the dehydrating agent is equal to or more than these lower limits, curing during storage can be easily suppressed, and when the content of the dehydrating agent is equal to or less than these upper limits, a decrease in the curability of the thermally conductive composition due to the dehydrating agent can be made less likely to occur.

[0050] <Silanol condensation catalyst> The thermally conductive composition according to the first embodiment of the present invention may contain a silanol condensation catalyst. When the thermally conductive composition of the present invention contains water, adding a silanol condensation catalyst may cause a condensation reaction of the organic polymer having a hydrolyzable silyl group during storage, potentially reducing storage stability. Therefore, the silanol condensation catalyst is preferably added immediately before use. The silanol condensation catalyst is preferably contained in the first agent, which will be described later.

[0051] Examples of silanol condensation catalysts include organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate)oxide, dibutyltin bis(acetylacetonate), dibutyltin bis(monoester maleate), tin octoate, dibutyltin octoate, dioctyltin oxide, dioctyltin diversatate, dioctyltin distearate, dibutyltin bis(triethoxysilicate), bis(dibutyltin bistriethoxysilicate)oxide, dibutyltin oxybisethoxysilicate, and 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, and organotitanium compounds such as tetra-n-butoxytitanate and tetraisopropoxytitanate. These silanol condensation catalysts may be used alone or in combination of two or more. Of the above-mentioned silanol condensation catalysts, organotin compounds are preferred, and dibutyltin dilaurate is more preferred.

[0052] The content of the silanol condensation catalyst in the thermally conductive composition is preferably 1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the organic polymer containing a hydrolyzable silyl group. The content of the silanol condensation catalyst in the first agent described below is also preferably within this range. When the content of the silanol condensation catalyst is equal to or greater than these lower limits, the curing rate can be increased, and when the content of the silanol condensation catalyst is equal to or less than these upper limits, a decrease in the storage stability of the composition can be suppressed.

[0053] The thermally conductive composition may contain additives other than those mentioned above (other additives), such as an ion scavenger, a thixotropic agent, an antioxidant, an ultraviolet absorber, a dispersant, a colorant such as a pigment or dye, an anti-settling agent, a solvent, a compatibilizer, etc. Examples of the compatibilizer include lower alcohols such as butyl carbitol, ethanol, and isopropanol.

[0054] <Two-component curing thermally conductive composition> The thermally conductive composition according to the first embodiment of the present invention may be used as a one-component type, or as a two-component type consisting of a combination of a first part and a second part, but is preferably used as a two-component type. In the case of a two-component type, good storage stability can be achieved. In particular, good storage stability can be achieved by blending the first part and the second part as follows.

[0055] The first agent preferably contains a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler, but does not contain an organic polymer having a hydrolyzable silyl group.The second agent preferably contains an organic polymer having a hydrolyzable silyl group, a plasticizer, a thermally conductive filler, and water, but does not contain an alkoxysilane having an amino group or a partial condensate thereof.

[0056] Details of the plasticizer, alkoxysilane having an amino group or its partial condensate, and thermally conductive filler contained in the first agent are as described above. The first agent may contain the silanol catalyst described above as needed, and may further contain the dehydrating agent described above as needed. On the other hand, it is preferable that the second agent does not contain a silanol catalyst or a dehydrating agent. Details of the organic polymer having a hydrolyzable silyl group, plasticizer, thermally conductive filler, and water contained in the second agent are as described above. Furthermore, when using the other additives described above, it is preferable that the other additives are also contained in either or both of the first agent and the second agent.

[0057] Furthermore, it is preferable that the first agent be substantially free of water. Here, "substantially free of water" means that the first agent may contain a small amount of water that is inevitably mixed in. Specifically, the first agent may contain water, for example, in an amount less than 10,000 ppm based on the total amount of the first agent, preferably 7,000 ppm or less, more preferably 4,000 ppm or less, even more preferably 3,000 ppm or less, and even more preferably 1,500 ppm or less. The water content of the first agent based on the total amount of the first agent should be lower than the water content of the second agent based on the total amount of the second agent. Reducing the water content of the first agent makes it easier to prevent the amino-containing alkoxysilane and its partial condensate from reacting with the thermally conductive filler, etc., in the first agent. This prevents thickening during storage and a decrease in flexibility when cured after long-term storage. The first agent does not need to contain water; the lower the water content of the first agent, the better, with the lower limit being 0 ppm.

[0058] When the thermally conductive composition is used as a two-component composition, a thermally conductive member made of a cured product of the two-component curing type thermally conductive composition can be formed by curing a composition obtained by mixing the first and second components during use.

[0059] The volume ratio of the first agent to the second agent (second agent / first agent) is preferably 1 or a value close to 1, specifically preferably 0.9 to 1.1, and more preferably 0.95 to 1.05. In this way, by setting the volume ratio of the first agent to the second agent to a value close to 1, it becomes easy to prepare a mixture of the first agent and the second agent.

[0060] The first and second agents may be filled in separate containers, specifically, the first agent in the first container and the second agent in the second container. The first and second containers may be separate or integrated. By integrating the first and second containers, it becomes easier to supply the first and second agents as a container set to the consumer. In this specification, the first container filled with the first agent and the second container filled with the second agent are collectively referred to as a container set.

[0061] Examples of containers include, but are not limited to, syringes, cartridges, pails, drums, and the like. For example, when filling a syringe, it is preferable to use a two-liquid parallel type syringe. As shown in FIG. 1 , a two-liquid parallel type syringe 30 is an integrated syringe in which a first syringe 31 constituting a first container and a second syringe 32 constituting a second container are arranged in parallel. The first agent 35 and the second agent 36 filled in the syringes 31 and 32 are preferably discharged from the syringes as dispensers and mixed.

[0062] When cartridges are used, the container set comprises a first cartridge constituting the first container and a second cartridge constituting the second container, and these cartridges may be integrated. The cartridges are usually set in syringes (e.g., a first syringe and a second syringe), and the first agent delivered from the first cartridge and the second agent delivered from the second cartridge are preferably discharged from the respective outlets of the first syringe and the second syringe, using each syringe as a dispenser, and then mixed.

[0063] The first and second agents may be mixed using a mixer such as a static mixer. As shown in FIG. 1 , the static mixer 38 is connected to the outlet 31A of the first syringe 31 and the outlet 32A of the second syringe 32, and the first agent 35 and the second agent 36 discharged from the outlets 31A and 32A can be mixed inside the mixer 38. The mixture (composition) obtained by mixing in the mixer 38 may be discharged from the outlet 39 of the mixer 38. Each syringe 31, 32 may have a structure in which the openings of barrels 33A, 34A, into which the first agent 35 and the second agent 36, respectively, are filled, are closed by lids 33B, 34B. In the syringe 30 shown in FIG. 1, the first agent 35 and the second agent 36 are preferably ejected from the respective outlets 31A and 32A after the respective lids 33B and 34B are removed and the first agent 35 and the second agent 36 are pushed out by pistons (not shown) inserted from the openings.

[0064] 2, the container set may include a first pail 41 that constitutes the first container and is filled with a first agent 45, and a second pail 42 that constitutes the second container and is filled with a second agent 46. Each pail 41, 42 may include, for example, a container body 43A, 44A that has an opening and is filled with the first agent 45 and the second agent 46, and a lid 43B, 44B that closes the opening of each container body 43A, 44A.

[0065] When the thermally conductive composition according to the first embodiment of the present invention is measured on the surface of a cured product by TOF-SIMS, the mz59 / total peak intensity is preferably 0.120 or less, more preferably 0.119 or less, and even more preferably 0.118 or less. When the mz59 / total peak intensity is below the upper limit, the specific amino group-containing structure derived from an alkoxysilane having an amino group or a partial condensate thereof is present in a certain amount or less on the surface of the cured product, making it easier to suppress reduction in elongation even when the cured product is exposed to a high temperature environment for a long period of time. Furthermore, from the viewpoint of easily imparting excellent adhesive strength to the cured product, the mz59 / total peak intensity is preferably 0.030 or more, more preferably 0.035 or more, and even more preferably 0.050 or more. The mz59 / total peak intensity can be adjusted, for example, by reducing the amount of alkoxysilane having an amino group or a partial condensate thereof added. Furthermore, the peak intensity can be reduced by increasing the blending amount of constituent materials such as organic polymers having hydrolyzable silyl groups, plasticizers, thermally conductive fillers, etc. To increase the peak intensity, the opposite adjustment to the above may be used.

[0066] When the surface of the thermally conductive composition according to the first embodiment of the present invention is measured by TOF-SIMS, the 59 / 55 peak intensity is preferably 5.13 or less, more preferably 5.12 or less, and even more preferably 5.11 or less. When the 59 / 55 peak intensity is below the upper limit, the amount of specific amino group-containing structures derived from the amino group-containing alkoxysilane or its partial condensate on the surface of the cured product is below a certain level, making it easier to suppress reduction in elongation even when the cured product is exposed to a high-temperature environment for a long period of time. Furthermore, from the viewpoint of easily imparting excellent adhesive strength to the cured product, the 59 / 55 peak intensity is preferably 2.00 or more, more preferably 2.50 or more, even more preferably 2.70 or more, and even more preferably 3.00 or more. The 59 / 55 peak intensity can be adjusted, for example, by reducing the amount of amino group-containing alkoxysilane or its partial condensate added. Furthermore, the peak intensity can be reduced by increasing the blending amount of the organic polymer having a polypropylene glycol structure as the main skeleton and a hydrolyzable silyl group. To increase the peak intensity, the above-mentioned adjustment can be carried out in the opposite manner.

[0067] When the surface of the cured product of the thermally conductive composition according to the first embodiment of the present invention is measured by TOF-SIMS, the mz45 / total peak intensity is preferably 0.0107 or less, more preferably 0.0105 or less, and even more preferably 0.0104 or less. The mz45 / total peak intensity is preferably 0.001 or more, more preferably 0.003 or more, and even more preferably 0.005 or more.

[0068] When the surface of the cured product of the thermally conductive composition according to the first embodiment of the present invention is measured by TOF-SIMS, the 45 / 55 peak intensity is preferably 0.452 or less, more preferably 0.451 or less, and even more preferably 0.450 or less. When the mz45 / total peak intensity is equal to or less than the upper limit, the mz45 / total peak intensity is preferably 0.100 or more, more preferably 0.250 or more, and even more preferably 0.300 or more. When the mz45 / total peak intensity and the 45 / 55 peak intensity are within the above ranges, both adhesiveness and curability are easily achieved. The mz45 / total peak intensity can be adjusted by, for example, reducing the amount of alkoxysilane or its partial condensate having an amino group. Furthermore, the peak intensity can be reduced by increasing the amount of constituent materials such as an organic polymer having a hydrolyzable silyl group, a plasticizer, and a thermally conductive filler. If it is desired to increase the peak intensity, it is advisable to make the opposite adjustment to the above. The peak intensity of 45 / 55 can be reduced, for example, by reducing the amount of alkoxysilane or its partial condensate having an amino group added. Furthermore, the peak intensity can be reduced by increasing the blending amount of an organic polymer having a polypropylene glycol structure as the main skeleton and a hydrolyzable silyl group. If it is desired to increase the peak intensity, it is advisable to make the opposite adjustment to the above.

[0069] <Elongation Change Rate> In the thermally conductive composition according to the first embodiment of the present invention, the cured product preferably has an elongation change rate of −0.5 or greater, more preferably −0.3 or greater, and even more preferably −0.2 or greater. When the elongation change rate of the cured product is equal to or greater than the above-mentioned lower limit, it can be said that a decrease in elongation can be suppressed even when the cured product is exposed to a high-temperature environment for a long period of time. The upper limit of the elongation change rate of the cured product is not particularly limited, but from the viewpoint of ease of handling, it is preferable that the upper limit be 0.5 or less, and preferably 0.3 or less. The elongation change rate of the cured product can be calculated using the following formula (1): Elongation Change Rate = (Elongation of Cured Product After Heating - Elongation of Cured Product Before Heating) / Elongation of Cured Product Before Heating (1). The elongation of the cured product is the elongation at which a 0.5 mm thick cured product breaks in a shear test, and heating is performed at 80°C for one week. Details of the method for measuring the elongation of the cured product before and after heating are as described in the Examples below.

[0070] <Initial elongation> The elongation (initial elongation) of the cured product of the thermally conductive composition according to the first embodiment of the present invention is preferably 0.5 mm or more, more preferably 0.7 mm or more, and even more preferably 0.8 mm or more. When the initial elongation is equal to or greater than the above-mentioned lower limit, the elongation of the cured product before heating can be said to be good, and the ability to conform to the adherend is likely to be improved. Furthermore, from the viewpoint of handleability, the initial elongation may be, for example, 2 mm or less, preferably 1.5 mm or less, and more preferably 1.2 mm or less. The initial elongation is the elongation at which a 0.5 mm thick cured product breaks in a shear test, and a detailed measurement method therefor is as described in the Examples below.

[0071] <Thermal Conductivity> The thermal conductive composition according to the first embodiment of the present invention preferably has a thermal conductivity of 1.0 W / m·K or more, more preferably 1.2 W / m·K or more, and even more preferably 1.4 W / m·K or more, of the cured product. A thermal conductivity of at least the above-mentioned lower limit indicates excellent thermal conductivity. The higher the thermal conductivity, the better. In practice, the thermal conductivity is, for example, 50 W / m·K or less, preferably 40 W / m·K or less. For example, when the thermal conductive composition is a two-component composition, the thermal conductivity can be measured by mixing the first and second components, leaving the mixture in an environment of 25°C and 50% RH for two weeks, and then curing the mixture to obtain a cured product. The thermal conductivity can be measured according to ASTM D5470-06. Specifically, the cured material is placed in a thickness greater than the actual thickness to be measured, covering the measurement die on the heating element side. The cured material is then sandwiched between heat sinks and compressed under a load of 30 psi until the cured material reaches a thickness of 1.0 mm, 1.5 mm, or 2.0 mm, and the thermal resistance is measured for each thickness. The thickness can be adjusted using spacers. A graph is created for these three thermal resistance values, with the horizontal axis representing thickness and the vertical axis representing thermal resistance value, and a three-point approximation line is determined using the least squares method. The slope of the approximation line is then used to determine the thermal conductivity.

[0072] Second Embodiment A thermally conductive composition according to another embodiment of the present invention (hereinafter also referred to as the second embodiment) includes an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler. The composition has a mz59 / total peak intensity of 0.120 or less, as determined by measuring the surface of the cured product using TOF-SIMS. When the mz59 / total peak intensity is 0.120 or less, the amount of specific amino group-containing structures derived from the amino group-containing alkoxysilane or its partial condensate on the surface of the cured product is below a certain level, thereby preventing a reduction in elongation even when the cured product is exposed to a high-temperature environment for a long period of time. From the above perspectives, in the second embodiment, the mz59 / total peak intensity is preferably 0.119 or less, and more preferably 0.118 or less. Furthermore, from the viewpoint of easily imparting excellent adhesive strength to the cured product, the peak intensity of mz59 / total is preferably 0.030 or more, more preferably 0.035 or more, and even more preferably 0.050 or more. The method for adjusting the peak intensity of mz59 / total is as explained in the first embodiment above, and therefore detailed explanation will be omitted.

[0073] Furthermore, in the thermally conductive composition according to the second embodiment of the present invention, when the surface of the cured product is measured by TOF-SIMS, the peak intensities of 59 / 55, mz45 / total, and 45 / 55 and the method for adjusting them are the same as those described in the first embodiment above, and therefore detailed description thereof will be omitted.

[0074] The thermally conductive composition according to the second embodiment of the present invention has an alkoxy group concentration of 0.00035 mol / cm ３ The alkoxy group concentration is preferably 0.00035 mol / cm or less. ３ When the alkoxy group concentration is 0.00032 mol / cm or less, reduction in elongation is more likely to be suppressed even when the thermal conductive member is exposed to a high-temperature environment for a long period of time. ３ It is preferable that the concentration is 0.00030 mol / cm or less. ３It is more preferable that the alkoxy group concentration is 0.00003 mol / cm or less. Note that the method for adjusting the alkoxy group concentration is as explained in the first embodiment, and therefore a detailed explanation will be omitted. In addition, the thermally conductive composition according to the second embodiment of the present invention has an alkoxy group concentration of 0.00003 mol / cm or less. ３ It is preferable that the concentration is 0.00005 mol / cm or more. ３ More preferably, it is 0.0001 mol / cm or more. ３ As the alkoxy group concentration increases, it becomes easier to impart excellent adhesive strength to the cured product of the thermally conductive composition, and interfacial peeling becomes less likely to occur.

[0075] A thermally conductive composition according to a second embodiment of the present invention includes an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler. In addition to these components, the composition may also include water, a dehydrating agent, a silanol condensation catalyst, and other additives. Since each of the above components is as described in the first embodiment, detailed description thereof will be omitted.

[0076] The thermally conductive composition according to the second embodiment of the present invention may be used as a one-component composition, as with the thermally conductive composition according to the first embodiment, or as a two-component composition consisting of a combination of a first component and a second component. However, from the viewpoint of storage stability, it is preferable to use the thermally conductive composition as a two-component composition. When using the thermally conductive composition as a two-component composition, as with the first embodiment, a thermally conductive member consisting of a cured product of the two-component curing thermally conductive composition can be formed by curing the composition obtained by mixing the first component and the second component, as with the first embodiment. The formulation, volume ratio, and mixing method of the first component and the second component are as described in the first embodiment above, and therefore detailed description thereof will be omitted.

[0077] When the thermally conductive composition is a two-component type, it is preferable that the two components are filled in separate containers, as in the first embodiment, specifically, the first component is filled in the first container and the second component is filled in the second container. The first and second containers are as described in the first embodiment above, so detailed descriptions thereof will be omitted. Furthermore, the thermally conductive composition according to the second embodiment of the present invention has the same elongation change rate, initial elongation, and thermal conductivity of the cured product as those described in the first embodiment above, so detailed descriptions thereof will be omitted.

[0078] <Thermal Conductive Member> When the thermally conductive composition of the present invention is a one-component type, the thermally conductive composition can be cured to form a cured product, thereby forming a thermally conductive member. In the case of a two-component curing thermally conductive composition, the first and second components are mixed and cured to form a cured product, thereby forming a thermally conductive member. The thermally conductive member may be disposed between two components, such as a heat generating element and a heat dissipating element. Examples of the heat generating element include electronic components that generate heat, such as a battery. Examples of the heat dissipating element include a housing and cooling components, such as a heat sink or a cooling plate.

[0079] [Applications] The thermally conductive composition and thermally conductive member of the present invention can be used in a variety of applications, for example, as a heat dissipation material for battery assemblies such as lithium-ion battery (LiB) assemblies, and can also be used in various electronic device applications such as power electronic devices, electronic packaging, LEDs, solar cells, and electric grids. Among these, they are preferably used in battery assemblies, and more preferably in LiB assemblies. Therefore, a preferred embodiment of the present invention provides a battery assembly including the above-described thermally conductive member. Note that battery assemblies such as LiB assemblies can be preferably used in automobiles such as electric vehicles.

[0080] In battery assembly applications, the thermally conductive composition, two-component curing thermally conductive composition, and thermally conductive member of the present invention are preferably used as a gap filler in a battery assembly. In one aspect, the thermally conductive composition and thermally conductive member of the present invention are preferably used in a battery module, and more preferably as a gap filler in a battery module. An example in which the thermally conductive member of the present invention is applied to a battery module will be described below.

[0081] In one embodiment, the battery module includes a gap material made of a thermally conductive material, a plurality of battery cells, and a module housing that houses the plurality of battery cells, the gap material being disposed inside the module housing. The gap material made of a thermally conductive material is filled between the battery cells and between the battery cells and the module housing, and the filled gap material is in close contact with the battery cells and the module housing. As a result, the gap material between the battery cells has the function of maintaining a separation between the battery cells. Furthermore, the gap material between the battery cells and the module housing is in close contact with both the battery cells and the module housing, and has the function of transferring heat generated in the battery cells to the module housing.

[0082] FIG. 3 shows a specific configuration of a battery module. FIG. 4 shows a specific configuration of each battery cell. As shown in FIG. 3, multiple battery cells 11 are arranged inside the battery module 10. Each battery cell 11 is laminated and encapsulated in a flexible exterior film, and has an overall shape of a flat body that is thin compared to its height and width. As shown in FIG. 4, such a battery cell 11 may have a positive electrode 11a and a negative electrode 11b exposed to the outside, and a central portion 11c of the flat surface may be thicker than the crimped end portion 11d. It is also preferable that the surface of each battery cell 11 be coated with a resin material. Coating the surface of each battery cell 11 with a resin material makes it easier to ensure insulation. The resin material is not particularly limited, but examples include polyester resins such as PET (polyethylene terephthalate), polyimide resins, olefin resins such as polypropylene resins, and polycarbonate resins. Among these, PET is more preferable.

[0083] As shown in Fig. 3, the battery cells 11 are arranged so that their flat surfaces face each other. In the configuration of Fig. 3, the gap material 13 is not filled so as to entirely cover the plurality of battery cells 11 housed inside the module housing 12. The gap material 13 is filled so as to fill gaps that exist in a portion (bottom portion) inside the module housing 12. The gap material 13 is filled between the battery cells 11 and between the battery cells 11 and the module housing 12, and is in close contact with the surfaces of the battery cells 11 in these portions and the inner surface of the module housing 12.

[0084] The gap material 13 filled between the battery cells 11 is adhered to the surfaces of both battery cells 11. However, the gap material 13 itself has appropriate elasticity and flexibility, so that even if an external force that displaces the spacing between the battery cells 11 is applied, it can mitigate distortion and deformation due to the external force. Therefore, the gap material 13 has the function of maintaining the separation between the battery cells 11. The gap material 13 filled in the gap between the battery cell 11 and the inner surface of the module housing 12 is also tightly adhered to the surface of the battery cell 11 and the inner surface of the module housing 12. As a result, heat generated inside the battery cell 11 is conducted via the gap material 13 adhered to the surface of the battery cell 11 to the inner surface of the module housing 12, which is in close contact with the other surface of the gap material 13.

[0085] The gap material 13 can be formed in the battery module 10 by applying a mixture (composition) of a thermally conductive composition or a first and second component of a two-component curing thermally conductive composition using a general dispenser, followed by curing. It is preferable to use a two-component curing thermally conductive composition when forming the gap material 13. Two-component compositions are easy to store, and if mixed immediately before use, they are less likely to harden during application with a dispenser, allowing them to harden quickly after application. Dispenser application is also preferable because it allows the composition to be filled relatively deep within the housing 12 of the battery module 10.

[0086] The gap material 13 covering the battery cells 11 preferably covers 20 to 40% of each battery cell 11 on one side of the battery cell 11. By covering 20% ​​or more, the battery cells 11 can be stably held. Furthermore, by sufficiently covering battery cells that generate a large amount of heat, heat dissipation efficiency is improved. On the other hand, by covering 40% or less, heat generated from the battery cells 11 can be efficiently dissipated, preventing weight increases and deterioration of workability. Furthermore, to improve heat dissipation efficiency, it is preferable to cover the side of the battery cells 11 where the electrodes 11a and 11b are located with the gap material 13, and it is more preferable to cover the entire electrodes 11a and 11b with the gap material 13. As described above, the battery module 10 can dissipate heat generated from the battery cells 11 to the module housing 12 via the gap material 13.

[0087] The gap material 13 is also preferably used in a battery pack having a plurality of battery modules 10 therein. A battery pack generally includes a plurality of battery modules 10 and a battery pack housing that houses the plurality of battery modules 10. In the battery pack, the gap material 13 can be provided between the battery modules 10 and the battery pack housing. This allows the heat dissipated to the module housing 12 as described above to be further dissipated to the battery pack housing, enabling effective heat dissipation.

[0088] In addition, in the above description, examples of the battery assembly have been described as a battery module or a battery pack including a battery module, but the battery assembly may also be applied to a battery assembly that does not include a battery module, and it is also preferable to apply the battery assembly to, for example, a battery assembly having a cell-to-pack structure.

[0089] A schematic diagram of a battery assembly having a cell-to-pack structure is shown in Figure 5. A battery assembly 20 having a cell-to-pack structure includes a plurality of battery cells 21 and a battery pack housing. The plurality of battery cells 21 are bonded to a base member 25 constituting the battery pack housing via a gap material 23 made of a thermally conductive material. The base member 25 may constitute a cooling plate or the like. The base member 25 made of a cooling plate or the like may have an uneven surface, and the battery cells 21 may be bonded to the uneven surface of the base member 25 via the gap material 23. The gap material 23 in the battery assembly 20 may be formed in the same manner as the gap material 13 in the battery module described above, for example, by using a general dispenser.

[0090] In the above description, an example has been described in which the surfaces of the battery cells 11, 21 are coated with a resin material, but components other than the battery cells, such as base members such as a cooling plate, a battery module, a module housing, and a housing for a battery pack, may also be coated with or made of a resin material. Even in this case, the components can be appropriately bonded to each other by using the thermally conductive member of the present invention as a gap material disposed between the components.

[0091] 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.

[0092] In this example, the evaluation was carried out by the following method.

[0093] <Alkoxy Group Concentration> The alkoxy group concentration was calculated by dividing the total number of moles of alkoxy groups contained in the alkoxysilane having an amino group and its condensate by the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group and its condensate.

[0094] <TOF-SIMS> Measurements using TOF-SIMS were carried out according to the following procedure. Note that TOF-SIMS measurements were not carried out in Example 5 and Comparative Example 4. (1) The thermally conductive composition of each Example and Comparative Example was applied to a cationic electrodeposition coated substrate ("SPCC-SD", manufactured by Nippon Test Panel Co., Ltd.) and left to cure at 25°C for two weeks. Thereafter, the cationic electrodeposition coated substrate to which the composition had been applied was frozen in liquid nitrogen for three minutes, and in the frozen state, the cured product of the thermally conductive composition (test piece) was peeled off from the cationic electrodeposition coated substrate. (2) The surface of the test piece peeled off in (1) above (the interface that had been in contact with the cationic electrodeposition coated substrate) was measured. Specifically, the following operations (2-1) to (2-3) were carried out based on the obtained secondary ion spectrum. (2-1) C ３ H ７ O+ and C ２ H ７ N ２ The area of ​​the peak containing the mass of +, that is, the peak area (a) in the region of m / z 59.030 to 59.80, was calculated by dividing it by the peak area (b) of the total secondary ions, and this was taken as the peak intensity of mz59 / total. ３ H ７ O+ and C ２ H ７ N ２ + indicates a structure derived from an alkoxysilane having an amino group. (2-2) C ３ H ５ The area of ​​the peak containing the mass of Si+, that is, the peak area (c) in the region of m / z 45.020 to 45.050, was calculated by dividing it by the peak area (b) of all secondary ions, and this was taken as the peak intensity of mz45 / total. ３ H ５ Si+ represents a structure derived from an alkoxysilane having an amino group. (2-3)C ３ H ７ The area of ​​the peak containing the mass of +, that is, the peak area (d) in the region of m / z 55.035 to 55.070, was calculated by dividing it by the peak area (b) of the total secondary ions, and this was taken as the peak intensity of mz55 / total. ３ H ７+ indicates a structure derived from polypropylene glycol that constitutes the main skeleton of the organic polymer having a hydrolyzable silyl group.

[0095] The above operations (2-1) to (2-3) were each repeated three times, and the average values ​​were calculated. The calculated average values ​​were designated as the peak intensity of mz59 / total, the peak intensity of mz45 / total, and the peak intensity of mz55 / total, respectively. Based on the peak intensities determined as above, 45 / 55 and 59 / 55 were calculated. Specifically, 45 / 55 was calculated by dividing the peak intensity of mz45 / total by the peak intensity of mz55 / total, and 59 / 55 was calculated by dividing the peak intensity of mz59 / total by the peak intensity of mz55 / total.

[0096] The measurement was performed using a TOF-SIMS 5 (manufactured by ION TOF) under the following conditions: (Measurement conditions) Primary ions: Bi ３＋＋ Primary ion energy: 25 kV Secondary ion polarity: positive Raster size: 500 μm square, and a 100 μm square near the center was analyzed Number of scans: 25 scans Number of pixels: 128 pixels Mass range (m / z): 0 to 850

[0097] <Adhesion Strength and Elongation> A shear test was conducted in accordance with DIN EN 1465 using the following method to measure the adhesion strength and elongation of the cured product. First, two cationic electrodeposition coated substrates ("SPCC-SD," manufactured by Nippon Test Panel Co., Ltd.) measuring 25 mm wide, 100 mm long, and 2 mm thick were prepared. A thermally conductive composition was applied to the longitudinal edge of one of the substrates, covering the entire width of the substrate and a length of 15 mm, resulting in a thickness of 0.5 mm after curing. The longitudinal edge of the other substrate was then placed on top of the applied thermally conductive composition, and the substrate was left in this state for two weeks in a 25°C environment to cure the thermally conductive composition, yielding two cured products that served as measurement samples. One of the obtained measurement samples was subjected to a tensile shear test in which the measurement sample was pulled in the longitudinal direction at a tensile speed of 10 mm / min in a 25°C, 50% RH environment until breakage, and the strength and elongation at breakage were measured. Another of the obtained measurement samples was heated in an 80°C environment for one week, and then subjected to a tensile shear test in the same manner as above to measure the strength and elongation at break. Two samples were prepared, and each measurement was calculated as an average of n = 2. In this measurement, the strength at break was defined as "adhesive strength" (shear adhesive strength), and the elongation at break was defined as "elongation" (shear elongation). The tensile shear test was performed using an Instron "68TM-30," and elongation was measured using a camera (Instron "AVE 2"). In Tables 1 and 2, the strength and elongation at break measured using a cured product that had not been heated in an 80°C environment for one week are referred to as "adhesive strength (initial)" and "elongation (initial)," respectively. The strength and elongation at break measured using a heated cured product are referred to as "adhesive strength (after heating)" and "elongation (after heating)," respectively. Furthermore, the percentage change in strength and elongation at break was calculated based on the measurements of the cured product before and after heating. Specifically, the respective rates of change were determined by subtracting the measured value before heating from the measured value after heating and dividing the resulting value by the measured value before heating.

[0098] <Fracture Mode> The fractured portions of the measurement samples after the tensile shear test were observed, and the fracture modes were classified as follows. The measurement samples were both heated and unheated during the tensile shear test. In Tables 1 and 2, the fracture modes evaluated using the unheated cured product are referred to as "fracture mode (initial)," and the fracture modes evaluated using the heated cured product are referred to as "fracture mode (after heating)." A: Peeling occurred in less than 20% of the interface area of ​​the thermally conductive composition, and in another area less than 50% of the area, there were areas where the adherend was visible, even though the peeling did not occur. B: Peeling occurred in less than 20% of the interface area of ​​the thermally conductive composition, and in another area 50% or more of the area, there were areas where the adherend was visible, even though the peeling did not occur. C: Peeling occurred in 20% or more but less than 50% of the interface area of ​​the thermally conductive composition. D: Peeling was observed in an area of ​​50% or more of the interface area of ​​the thermally conductive composition.

[0099] <Overall evaluation> A: Elongation (initial) is 1.0 mm or more, and the rate of change in elongation is -0.25 or more. B: Elongation (initial) is 0.9 mm or more and less than 1.0 mm, and the rate of change in elongation is -0.25 or more, or elongation is 0.7 mm or more and less than 0.9 mm, and the reduction in elongation is 0.1 or more. C: Elongation (initial) is 0.7 mm or more and less than 0.9 mm, and the rate of change in elongation is -0.1 or more and less than 0.1. D: Elongation (initial) is less than 0.7 mm, or elongation is 0.7 mm or more and less than 0.9 mm, and the rate of change in elongation is -0.1 or less, or the rate of change in elongation is less than -0.25.

[0100] In the examples and comparative examples, the following components were used.

[0101] <Curable liquid resin> Kaneka Corporation "MS Polymer S327", number average molecular weight 25,000, linear type, terminal silylation rate 68%, specific gravity 1 g / cm ３, an organic polymer having a hydrolyzable silyl group (an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide) - Kaneka Corporation "MS Polymer S303", number average molecular weight 25,000, branched type, terminal silylation rate 45%, specific gravity 1 g / cm ３ , an organic polymer having a hydrolyzable silyl group (an organic polymer having a dimethoxymethylsilyl group at the end of a branched polypropylene oxide) - Kaneka Corporation "MS Polymer SAX220", number average molecular weight 27,000, linear type, terminal silylation rate 80%, specific gravity 1 g / cm ３ , an organic polymer having a hydrolyzable silyl group (an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide)

[0102] <Plasticizer> 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH), specific gravity 0.97 g / cm ３

[0103] <Alkoxysilane having an amino group> N-(2-aminoethyl)-3-aminopropyltrimethoxysilane "KBM-603" manufactured by Shin-Etsu Silicones Co., Ltd. <Partial condensate of alkoxysilane having an amino group> Alkoxysilane oligomer which is a hydrolysis condensate of ethyltriethoxysilane and 3-[N-(2-aminoethyl)amino]propyltriethoxysilane "Dynasylane 1146" manufactured by Evonik

[0104] <Thermal conductive filler> Aluminum hydroxide 1: average particle size 1 μm Aluminum hydroxide 2: average particle size 1 μm, surface treated with stearic acid Aluminum hydroxide 3: average particle size 10 μm Aluminum hydroxide 4: average particle size 100 μm Aluminum oxide 1: average particle size 12.5 μm Aluminum oxide 2: average particle size 71.6 μm

[0105] <Additives> Dehydrating agent: vinyltrimethoxysilane "KBM-1003" manufactured by Shin-Etsu Silicones Co., Ltd. Silanol condensation catalyst: dibutyltin dilaurate, water, dispersant: "DISPERBYK-106" manufactured by BYK-Chemie Co., Ltd. Antioxidant: "SONGNOX1010" manufactured by Songwon Co., Ltd. Thixotropic agent: "T-1800" manufactured by Ito Oil Mills Co., Ltd. Ion scavenger: "IXE100" manufactured by Toagosei Co., Ltd.

[0106] Example 1 A first part was prepared by mixing a plasticizer, aluminum hydroxide 1, aluminum hydroxide 3, aluminum hydroxide 4, aluminum oxide 1, a dehydrating agent, an alkoxysilane having an amino group, and a silanol condensation catalyst according to the formulation in Table 1. A second part was prepared by mixing an organic polymer having a hydrolyzable silyl group, a plasticizer, aluminum hydroxide 1, aluminum hydroxide 3, aluminum hydroxide 4, aluminum oxide 1, water, and an antioxidant according to the formulation in Table 1. The first and second parts were then mixed in the volume ratio shown in Table 1 to prepare a thermally conductive composition. Various measurements and evaluations were performed on the obtained thermally conductive composition.

[0107] [Examples 2 to 9, Comparative Examples 1 to 5] Thermally conductive compositions were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed according to Tables 1 and 2, and various measurements and evaluations were carried out.

[0108]

[0109] *In Tables 1 and 2, "modified silyl" refers to an organic polymer having a hydrolyzable silyl group, "aminosilane" refers to an alkoxysilane having an amino group and its partial condensate, and "vinylsilane" refers to a dehydrating agent. *In Tables 1 and 2, "the number of OMe derived from aminosilane per unit volume occupied by the liquid resin" refers to the alkoxy group concentration in this specification, and the detailed calculation method is as described above.

[0110] As is clear from the above results, the thermally conductive compositions prepared in the examples all had an alkoxy group concentration below a certain level, had good initial elongation, and were able to suppress a decrease in elongation even after the cured product was heated at high temperatures. In contrast, the thermally conductive compositions prepared in the comparative examples all had an alkoxy group concentration above a certain standard, and either had poor initial elongation or were unable to sufficiently suppress a decrease in elongation when heated at high temperatures. Similarly, the thermally conductive compositions prepared in the examples all had a peak intensity of mz59 / total below a certain level, had good initial elongation, and were able to suppress a decrease in elongation even after the cured product was heated at high temperatures. In contrast, the thermally conductive compositions prepared in the comparative examples all had a peak intensity of mz59 / total above a certain value, and therefore either had poor initial elongation or were unable to sufficiently suppress a decrease in elongation when heated at high temperatures.

[0111] REFERENCE SIGNS LIST 10 Battery module 11, 21 Battery cell 11a Electrode (positive electrode) 11b Electrode (negative electrode) 11c Center portion 11d End portion 12 Battery module housing (module housing) 13, 23 Gap material 20 Battery assembly 25 Base member 30 Syringe 31 First syringe 31A First syringe outlet 32 ​​Second syringe 32A Second syringe outlet 33A, 34A Barrel 33B, 34B Barrel lid 35, 45 First agent 36, 46 Second agent 38 Mixer 39 Mixer outlet 41 First pail 42 Second pail 43A, 44A Container body with opening 43B, 44B Lid for closing the opening of the container body

Claims

A thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler, The concentration of the alkoxy group of the alkoxysilane having an amino group relative to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof is 0.00035 mol / cm ３ A thermally conductive composition comprising: 　 A thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a plasticizer, an alkoxysilane having an amino group or a partial condensate thereof, and a thermally conductive filler, A thermally conductive composition, wherein the surface of a cured product of the thermally conductive composition is measured by TOF-SIMS and the peak intensity of mz59 / total is 0.120 or less. 　 The thermally conductive composition according to claim 1 or 2, comprising the alkoxysilane having an amino group. 　 a first agent filled in a first container, the first agent including the plasticizer, the alkoxysilane having an amino group or a partial condensate thereof, and the thermally conductive filler, and the first agent not including the organic polymer having a hydrolyzable silyl group; 3. The thermally conductive composition according to claim 1, wherein the second part contains the organic polymer having a hydrolyzable silyl group, the plasticizer, the thermally conductive filler, and water, but does not contain the alkoxysilane having an amino group or a partial condensate thereof, and is filled in a second container. 　 The thermally conductive composition according to claim 1 or 2, wherein the organic polymer having a hydrolyzable silyl group is linear.

3. The thermally conductive composition according to claim 1, wherein the organic polymer having a hydrolyzable silyl group has a number average molecular weight of 1,000 or more. 　 The thermally conductive composition according to claim 1 or 2, wherein the content of the thermally conductive filler is 65% by volume or less based on the total volume of the thermally conductive composition. 　 The thermally conductive composition of claim 1 or 2, wherein the thermally conductive filler comprises aluminum hydroxide. 　 The thermally conductive composition of claim 1 or 2, wherein the thermally conductive filler comprises aluminum oxide.

3. The thermally conductive composition according to claim 1, wherein a cured product of the thermally conductive composition has a thermal conductivity of 1.0 W / m·K or more.

3. The thermally conductive composition according to claim 1, wherein the alkoxysilane having an amino group or a partial condensate thereof has three or more alkoxy groups in one molecule. 　 The concentration of the alkoxy group of the alkoxysilane having an amino group is 0.00003 mol / cm ３ The thermally conductive composition according to claim 1 or 2, wherein 　 3. The thermally conductive composition according to claim 1, wherein the surface of a cured product of the thermally conductive composition is measured by TOF-SIMS and the peak intensity of mz59 / total is 0.030 or more.

2. The thermally conductive composition according to claim 1, wherein the surface of the cured product of the thermally conductive composition is measured by TOF-SIMS and the peak intensity of mz59 / total is 0.120 or less. 　 The concentration of the alkoxy group of the alkoxysilane having an amino group relative to the total volume of the organic polymer having a hydrolyzable silyl group, the plasticizer, and the alkoxysilane having an amino group or a partial condensate thereof is 0.00035 mol / cm ３ 3. The thermally conductive composition of claim 2, wherein: 　 A thermally conductive member comprising a cured product of the thermally conductive composition according to claim 1 or 2. 　 A battery assembly comprising the thermally conductive member of claim 16.

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