Two-component curable thermally-conductive composition, method for producing same, thermally-conductive member, and battery assembly

Abstract

A two-component curable thermally-conductive composition according to the present invention comprises: an organic polymer having a hydrolyzable silyl group; a thermally-conductive filler; an aminosilane; and water. The two-component curable thermally conductive composition further comprises: a first agent that contains the organic polymer and the water, is substantially free of the aminosilane, and is filled into a first container; and a second agent that contains the aminosilane, is substantially free of water, is substantially free of the organic polymer, and is filled into a second container.

Description

Two-component curing thermally conductive composition, its manufacturing method, thermally conductive member, and battery assembly

[0001] The present invention relates to a two-component curing thermally conductive composition, a thermally conductive member, a battery assembly, and a method for producing the two-component curing thermally conductive composition.

[0002] Two-component curable thermally conductive compositions containing a thermally conductive filler are widely known as curable liquid compositions. For example, they are filled between a heat generating element and a heat sink, and then cured to form a cured product, which is used as a thermally conductive member such as a heat dissipating gap filler that transfers heat generated by the heat generating element to the heat sink.

[0003] In recent years, amid a market backdrop of steady growth in the production volume of electric vehicles (EVs), there has been an increasing demand for two-component, room-temperature curing heat-dissipating gap fillers for lithium-ion batteries (LiBs).From the viewpoint of heat dissipation, in lithium-ion batteries, two-component curing thermally conductive compositions are often filled between components such as battery cells, battery modules, and battery packs in order to fix the components together and to improve heat dissipation.

[0004] For example, Patent Document 1 discloses a two-component curing thermally conductive composition comprising a first part containing a catalyst, a ceramic filler, a low-volatility organic liquid, and water, and a second part containing a silyl-modified reactive polymer, a low-volatility organic liquid, and a ceramic filler. In this composition, the low-volatility organic liquid is present in an amount greater than about 50 wt % based on the total weight of the silyl-modified reactive polymer. Furthermore, this composition also discloses that the second part may contain a silane compound, such as alkyltrimethoxysilane or vinyltrimethoxysilane, as a water scavenger.

[0005] Patent Document 2 discloses a curable composition containing a polyoxyalkylene polymer having a reactive silicon group, a (meth)acrylic acid ester copolymer having a reactive silicon group, and a filler. This composition is described as being a two-component composition consisting of a base resin containing a polyoxyalkylene polymer and a (meth)acrylic acid ester copolymer, and a curing agent containing components such as a silanol condensation catalyst, a filler, a plasticizer, and water. It is described that an adhesion promoter such as a silane coupling agent can be blended into the curable composition, and it is also described that a silane coupling agent can be blended into the base resin.

[0006] JP 2022-521790 A JP 2023-100591 A

[0007] In recent years, LiBs have become increasingly sophisticated, enabling rapid charging. As LiBs become more sophisticated, they can experience significant thermal expansion. Therefore, the two-component curing thermally conductive compositions used between the LiB and various components face challenges in terms of their ability to accommodate the LiB's thermal expansion. Two major approaches to address this issue have been proposed. The first is to improve the thermal conductivity of the cured product of the two-component curing thermally conductive composition, thereby suppressing the LiB's thermal expansion. The second is to impart high elongation and flexibility to the cured product of the composition, allowing it to accommodate shear displacement during thermal expansion. The former requires a high thermal conductivity, which requires a high filling rate of the thermally conductive filler. This reduces the flexibility of the cured product, making it susceptible to cracking even with slight displacement. Therefore, the latter is preferable as a measure to accommodate thermal expansion.

[0008] As a means for developing the latter, it is conceivable to use a thermally conductive curable composition based on a silyl-modified reactive polymer, as described in Patent Document 1, for example. According to the inventors' studies, in order to achieve high flexibility, it is necessary to reduce the content of the silyl-modified reactive polymer in the overall composition, and it is also necessary to design the formulation so as to obtain a sufficient curing rate even when the resin content is low. Examples of compounds that accelerate the curing rate include various silane coupling agents, as described in Patent Document 2, and according to the inventors' studies, it has been found that amine silanes having an amino group, such as 3-aminopropyltrimethoxysilane, are particularly effective in accelerating the curing of thermally conductive curable compositions based on silyl-modified reactive polymers.

[0009] However, in the case of the two-component curing type described in Patent Document 2, there is a risk that the flexibility after curing may be deteriorated due to heating during dehydration or the like during production.

[0010] Therefore, an object of the present invention is to provide a two-component curable thermally conductive composition that can suppress deterioration of flexibility due to heating during the manufacturing process and also has good storage stability.

[0011] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by adjusting the components contained in the first and second parts of a two-component curing thermally conductive composition containing an organic polymer having a hydrolyzable silyl group, a thermally conductive filler, an aminosilane, and water, and have completed the present invention as described below. That is, the present invention provides the following [1] to

[14] .

[0012] [1] A two-component curing thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a thermally conductive filler, an aminosilane, and water, the two-component curing thermally conductive composition comprising: a first part containing the organic polymer and the water but substantially free of the aminosilane, the first part being filled in a first container; and a second part containing the aminosilane, substantially free of water, and substantially free of the organic polymer, the second part being filled in a second container. [2] The two-component curing thermally conductive composition according to [1] above, wherein a 0.5 mm thick cured product obtained by mixing the first part and the second part and leaving it at 25°C for one week has a shear break elongation of 0.2 mm or more. [3] The two-component curing thermally conductive composition according to [1] or 2 above, wherein the organic polymer has a number average molecular weight of 1,000 or more. [4] The two-component curing thermally conductive composition according to any one of [1] to [3] above, wherein the content of the thermally conductive filler is 300 parts by mass or more and 3,000 parts by mass or less, relative to 100 parts by mass of the total of the organic polymer and plasticizer contained in the two-component curing thermally conductive composition. [5] The two-component curing thermally conductive composition according to any one of [1] to [4] above, wherein both the first and second components contain the thermally conductive filler. [6] The two-component curing thermally conductive composition according to any one of [1] to [5] above, wherein the second component has a viscosity increase rate of 190% or less after storage at 50°C for 3 days. [7] The two-component curing thermally conductive composition according to any one of [1] to [6] above, wherein the second component contains a plasticizer. [8] The two-component curing thermally conductive composition according to any one of [1] to [7] above, wherein the second component contains a silanol condensation catalyst. [9] A thermally conductive member comprising a cured product of the two-component curing thermally conductive composition according to any one of [1] to [8] above.

[10] A battery assembly comprising the thermally conductive member according to [9] above.

[11] A method for producing a two-component curing thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a thermally conductive filler, an aminosilane, and water, the method comprising the steps of: preparing a first part comprising the organic polymer and the water and substantially not containing the aminosilane; and preparing a second part comprising the aminosilane, substantially not containing water, and substantially not containing the organic polymer.

[12] The method for producing the two-component curing thermally conductive composition according to

[11] above, wherein the step of preparing the second part comprises the steps of: preparing a pre-composition that is substantially free of water and the organic polymer, and that contains the thermally conductive filler and a plasticizer; dehydrating the pre-composition; and adding an aminosilane to the pre-composition after dehydration.

[13] The method for producing the two-component curing thermally conductive composition according to

[12] above, wherein the pre-composition is dehydrated by heating.

[14] Use of the thermally conductive member according to [9] above as a heat dissipation material for a battery assembly.

[0013] According to the present invention, there is provided a two-component curable thermally conductive composition that can suppress deterioration of flexibility due to heating during the production process and also has good storage stability.

[0014] 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;

[0015] [Two-component curing thermally conductive composition] The two-component curing thermally conductive composition of the present invention comprises an organic polymer having a hydrolyzable silyl group (hereinafter sometimes simply referred to as "organic polymer (A)"), a thermally conductive filler, an aminosilane, and water. The two-component curing thermally conductive composition of the present invention is a combination of a first part and a second part, and the two-component curing thermally conductive composition is obtained by mixing the first part and the second part. The components contained in the two-component curing thermally conductive composition are mixed by sprinkling them appropriately on the first part and the second part. Specifically, the first part contains the organic polymer (A) and water, and is substantially free of aminosilane. On the other hand, the second part contains aminosilane, but is substantially free of water and organic polymer.

[0016] The two-component curing thermally conductive composition of the present invention has the above-described configuration. When the first and second components are mixed, the action of the aminosilane and water allows the organic polymer (A) to cure at an appropriate rate, ensuring the flexibility and adhesive strength of the cured product. Furthermore, by incorporating water into the first component containing the organic polymer (A) but substantially eliminating the aminosilane, and by substantially eliminating water and the organic polymer (A) from the second component containing the aminosilane, crosslinking of the organic polymer (A) due to the reaction of the aminosilane during storage can be prevented. Furthermore, by preventing the aminosilane from reacting with other components, such as the thermally conductive filler blended into the second component, due to the action of water during storage, thickening during storage is prevented, improving storage stability. Furthermore, the second component may be heated during production, for example, by thermal dehydration to reduce the amount of water inevitably mixed in. However, even when heated during production, side reactions due to heating can be prevented. Therefore, even if the second agent contains aminosilane, it is possible to prevent performance degradation such as a decrease in flexibility due to side reactions caused by heating.

[0017] Each component used in the two-component curing thermally conductive composition is described in detail below. <Organic Polymer (A)> The two-component curing thermally conductive composition of the present invention contains an organic polymer (organic polymer (A)) having a hydrolyzable silyl group. The hydrolyzable silyl group in the organic polymer is hydrolyzed by moisture to form a silanol group, and then the silanol groups undergo condensation polymerization with each other or with the hydrolyzable silyl group to form a siloxane bond. This causes the organic polymer to form a crosslinked structure, which hardens to yield a rubber-like elastomer. Note that a silanol group refers to a hydroxy group (Si—OH) directly bonded to a silicon atom.

[0018] 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 trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, and triphenoxysilyl groups; dialkoxysilyl groups such as dimethoxymethylsilyl and diethoxymethylsilyl groups; and monoalkoxysilyl groups such as methoxydimethylsilyl and ethoxydimethylsilyl groups. Of these, dialkoxysilyl groups are more preferred, and dimethoxymethylsilyl groups are particularly preferred.

[0019] The organic polymer (A) may have a linear or branched main chain, but preferably has a linear main chain. That is, the organic polymer (A) of the present invention preferably has a hydrolyzable silyl group at the end of the linear main chain, and preferably has hydrolyzable silyl groups at both ends of the main chain. When the organic polymer (A) is used at the end, the cured product becomes more easily extensible, increasing flexibility and improving conformability.

[0020] The terminal silylation rate of the organic polymer (A) is, for example, 55% or more, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the terminal silylation rate is a certain level or more, it becomes easier to appropriately adjust the curability and flexibility of the two-component curing thermally conductive composition. The terminal silylation rate means the proportion of silylated terminals to all terminals of the organic polymer (A). 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 (A) is １ It is determined by H-NMR.

[0021] The average number of hydrolyzable silyl groups in one molecule of the organic polymer (A) is preferably 1 to 3, more preferably 1.1 to 2.5, and even more preferably 1.3 to 2. When the number of hydrolyzable silyl groups in the polymer is within this range, the two-component curing thermally conductive composition has good curability and flexibility. The average number of hydrolyzable silyl groups in one molecule of the organic polymer (A) can be measured by the following method: １ It can be calculated based on the concentration of hydrolyzable silyl groups in the organic polymer (A) determined by H-NMR and the number average molecular weight of the organic polymer (A) determined by GPC.

[0022] The method for introducing a hydrolyzable silyl group into the organic polymer (A) 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 reacting a hydrosilane having a hydrolyzable silyl group with the organic polymer modified with an unsaturated group in the molecule, (2) a method in which a compound having a mercapto group and a hydrolyzable silyl group is reacted with the organic polymer modified with an unsaturated group in the molecule, 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.

[0023] The organic polymer is not particularly limited, and examples thereof include polyalkylene oxide polymers such as polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymers, and polypropylene oxide-polybutylene oxide copolymers; saturated hydrocarbon polymers; polyurethane; 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; and vinyl acetate. Examples of such polymers include vinyl polymers obtained by radical polymerization of monomers such as 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.

[0024] Among these, polyalkylene oxide polymers are preferred as the organic polymer from the viewpoint of improving adhesive strength and elongation after curing. That is, polyalkylene oxide polymers having a hydrolyzable silyl group are preferred as the organic polymer (A). Among polyalkylene oxides, polypropylene oxide is particularly preferred. The organic polymer (A) may be used alone or in combination of two or more.

[0025] The number average molecular weight (Mn) of the organic polymer (A) is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, even more preferably 10,000 or more, and preferably 70,000 or less, more preferably 40,000 or less, and even more preferably 35,000 or less. When the number average molecular weight of the organic polymer (A) is above these lower limits, the cured product of the two-component curing thermally conductive composition is prevented from becoming brittle, and the hardness and elongation of the cured product are improved, and the followability is also improved. Furthermore, when the number average molecular weight of the organic polymer (A) is below these upper limits, the viscosity of the resulting two-component curing thermally conductive composition is reduced, improving coatability. Furthermore, mechanical strength is also likely to be improved. Note that when the two-component curing thermally conductive composition contains multiple types of organic polymers (A), the above number average molecular weight (Mn) refers to the number average molecular weight (Mn) of all of them.

[0026] The number average molecular weight refers to a polystyrene-equivalent value measured by GPC (gel permeation chromatography). 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 a solvent, a column temperature of 40° C., and a flow rate of 0.3 ml / min.

[0027] Commercially available products can be used as the organic polymer (A). For example, polyalkylene oxide polymers having a dimethoxysilyl group at the end of the main chain skeleton include those manufactured by AGC under the product names "Excestar A2410" and "Excestar S4530," and those manufactured by Kaneka under the product names "MS Polymer S203H," "MS Polymer S203," "MS Polymer S327," "MS Polymer SAX010," "Silyl SAT350," and "SAX220." Other examples include "GENIOSIL STPE-35" manufactured by Wacker Chemical.

[0028] The content of the organic polymer (A) in the two-component curing thermally conductive composition is preferably 2% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and even more preferably 3.5% by mass or more and 15% by mass or less, based on the total content of the two-component curing thermally conductive composition. When the content of the organic polymer (A) is equal to or greater than the above lower limit, the thermally conductive filler can be appropriately retained by the organic polymer (A). Furthermore, various properties such as flexibility and adhesive strength can be easily imparted to the cured product of the two-component curing thermally conductive composition. Furthermore, when the content of the organic polymer (A) is equal to or less than the above upper limit, the thermally conductive filler can be appropriately contained, making it easier to improve the thermal conductivity of the cured product of the two-component curing thermally conductive composition. Note that the content in the two-component curing thermally conductive composition refers to the content when the first and second parts are mixed to obtain the two-component curing thermally conductive composition, and the same applies hereinafter.

[0029] As described above, the organic polymer (A) is contained in the first agent. The content of the organic polymer (A) in the first agent is not particularly limited, but is preferably 5% by mass or more and 60% by mass or less, more preferably 7% by mass or more and 35% by mass or less, and even more preferably 8% by mass or more and 25% by mass or less, relative to the total amount of the first agent. On the other hand, the organic polymer (A) is not substantially contained in the second agent. Here, "not substantially contained" means that the organic polymer (A) may be contained in a small amount as long as the effects of the present invention are achieved. For example, the content of the organic polymer (A) in the second agent may be less than 1% by mass, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, relative to the total amount of the second agent. It is most preferable that the second agent does not contain the organic polymer (A). That is, the content of the organic polymer (A) in the second agent is most preferably 0% by mass.

[0030] <Thermal Conductive Filler> The two-component curing thermally conductive composition of the present invention contains a thermally conductive filler. By including a thermally conductive filler in the two-component curing thermally conductive composition, the thermal conductivity of the two-component curing thermally conductive composition is improved.

[0031] 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 when improving heat dissipation and exhibiting flexibility, while aluminum hydroxide is preferred when improving flame retardancy or when reducing the specific gravity of the inorganic filler to reduce the weight of the two-component curing thermally conductive composition. Metal hydroxides such as aluminum hydroxide have hydroxyl groups, which makes them prone to side reactions when coexisting with an organic polymer (A), particularly an aminosilane and an organic polymer (A). However, in the present invention, since neither the first nor second agent substantially contains both an aminosilane and an organic polymer (A), side reactions are less likely to occur. The thermally conductive fillers described above may be used alone or in combination of two or more.

[0032] In order to achieve high thermal conductivity while keeping the specific gravity of the two-component curing thermally conductive composition low and reducing its weight, it is also preferable to use aluminum oxide and aluminum hydroxide in combination. When using these in combination, the ratio of the aluminum hydroxide content to the aluminum oxide content in the two-component curing thermally conductive composition, on a mass basis, is not particularly limited, but is, for example, 0.05 to 20, preferably 0.1 to 10, more preferably 0.12 to 5, and even more preferably 0.15 to 3.

[0033] 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 more 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. When a small-particle-size thermally conductive filler and a large-particle-size thermally conductive filler are used in combination, the ratio of the content of the small-particle-size thermally conductive filler to the content of the large-particle-size thermally conductive filler in the two-component curing thermally conductive composition is not particularly limited, but is, for example, 0.02 or more and 2 or less, preferably 0.05 or more and 1 or less, more preferably 0.1 or more and 0.8 or less, and even more preferably 0.15 or more and 0.6 or less, on a mass basis.

[0034] The content of the thermally conductive filler in the two-component curing thermally conductive composition is preferably 300 parts by mass or more and 3,000 parts by mass or less, more preferably 400 parts by mass or more and 2,000 parts by mass or less, even more preferably 450 parts by mass or more and 1,500 parts by mass or less, and even more preferably 500 parts by mass or more and 1,300 parts by mass or less, per 100 parts by mass of the total of the organic polymer (A) and the plasticizer. In the present invention, the two-component curing thermally conductive composition may not contain a plasticizer. In such a case, the total of the organic polymer (A) and the plasticizer refers to the content of the organic polymer (A). When the content of the thermally conductive filler is equal to or greater than the above-mentioned lower limit, a certain level of thermal conductivity can be imparted to the two-component curing thermally conductive composition. Furthermore, when the content of the thermally conductive filler is equal to or less than the above-mentioned upper limit, the thermally conductive filler can be appropriately dispersed in the two-component curing thermally conductive composition, and the viscosity of the two-component curing thermally conductive composition can be prevented from becoming unnecessarily high. Furthermore, the two-component curing thermally conductive composition tends to have good elongation and adhesive strength.

[0035] The content (filling rate) of the thermally conductive filler in the two-component curing thermally conductive composition is preferably 50% by volume or more and 90% by volume or less, more preferably 55% by volume or more and 85% by volume or less, even more preferably 58% by volume or more and 80% by volume or less, even more preferably 59% by volume or more and 75% by volume or less, and even more preferably 60% by volume or more and 70% by volume or less, based on the total volume of the two-component curing thermally conductive composition.

[0036] In the present invention, it is preferable that both the first and second agents contain a thermally conductive filler. The thermally conductive filler is preferably distributed in appropriate amounts to both the first and second agents so that the first and second agents can be mixed at a volume ratio of approximately 1:1, as described below. For example, the ratio of the thermally conductive filler content in the second agent to the thermally conductive filler content in the first agent (second agent / first agent) is not particularly limited by mass, but may be distributed so as to be, for example, approximately 0.1 to 10. However, as described above, since the first agent contains the organic polymer (A), it is preferable that a larger amount of the thermally conductive filler be distributed to the second agent. Therefore, the ratio (second agent / first agent) is preferably 0.5 to 5, more preferably 1 to 2, and even more preferably 1.1 to 1.8. The content of the thermally conductive filler contained in each agent referred to here refers to the amount of the thermally conductive filler contained in each agent before mixing the first and second agents to obtain the two-component curing thermally conductive composition.

[0037] <Aminosilane> Aminosilane is a silane compound having an amino group. When the two-component curing thermally conductive composition contains an aminosilane, curing is accelerated and various physical properties such as mechanical strength, flexibility, and adhesive strength tend to be improved. The aminosilane is preferably an alkoxysilane having an amino group. The aminosilane preferably has at least one of a primary amino group or a secondary amino group, more preferably a primary amino group, and also preferably an alkoxysilane having both a primary amino group and a secondary amino group.

[0038] 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, Examples of suitable aminosilanes include N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)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. Among these, those having a structure in which three alkoxy groups are bonded to one silicon atom are preferred, and more specifically, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is more preferred. The aminosilanes may be used alone or in combination of two or more.

[0039] The content of aminosilane in the two-component curing thermally conductive composition is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less, and even more preferably 2.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the organic polymer (A). The content of aminosilane in the second part is also preferably within the same range. The content of aminosilane in the second part refers to the amount relative to 100 parts by mass of the organic polymer (A) in the composition when the first part and the second part are mixed. When the content of aminosilane is equal to or greater than these lower limits, curing is promoted and various physical properties are easily improved. Furthermore, when the content of aminosilane is equal to or less than these upper limits, side reactions can be appropriately prevented, and deterioration of various performances can be suppressed.

[0040] While the aminosilane is contained in the second agent as described above, it is not substantially contained in the first agent. Here, "not substantially contained" means that the first agent may contain a trace amount of aminosilane. Specifically, if the content is, for example, about 500 ppm or less based on the total amount of the first agent (by mass), it may be contained without adversely affecting storage stability. The content of aminosilane in the first agent is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. The content of aminosilane in the first agent based on the total amount of the first agent is lower than the content of aminosilane in the second agent based on the total amount of the second agent. The less aminosilane in the first agent, the better, and it is most preferable that it is not contained in the first agent.

[0041] <Water> The two-component curing thermally conductive composition of the present invention contains water. By containing water, the two-component curing thermally conductive composition can promote the reaction between the organic polymers (A) and cure quickly, thereby improving various properties such as flexibility and adhesive strength of the cured product. Water is preferably blended into the first part. The amount of water in the first part is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 0.8 parts by mass or more and 15 parts by mass or less, and even 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 (A) blended in the first part. By ensuring that the amount of water is equal to or greater than the above lower limit, the reaction between the organic polymers (A) can be appropriately promoted. On the other hand, by ensuring that the amount of water is equal to or less than the above upper limit, the two-component curing thermally conductive composition can be cured at a curing speed commensurate with the blend amount.

[0042] On the other hand, the second agent is substantially free of water. Here, "substantially free of water" means that a small amount of water may be unavoidably mixed into the first agent. Specifically, the second agent may contain water in an amount of, for example, less than 10,000 ppm, 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, based on the total amount of the second agent (by mass). The water content of the second agent based on the total amount of the second agent is preferably lower than the water content of the first agent based on the total amount of the first agent. Reducing the water content of the second agent makes it easier to prevent the aminosilane in the second agent from reacting with the thermally conductive filler, etc. This makes it possible to prevent thickening during storage and a decrease in flexibility when cured after long-term storage. The lower the water content of the second agent, the better, with the lower limit being 0 ppm. However, it is practically difficult to completely prevent water absorption, so the water content may be, for example, 10 ppm or 50 ppm.

[0043] <Plasticizer> The two-component curing thermally conductive composition of the present invention preferably contains a plasticizer. The inclusion of a plasticizer can enhance the flexibility and elongation of the cured product. It also reduces the viscosity, improving workability. 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 polyalkylene oxides, organic phosphate plasticizers and organic phosphite plasticizers, and epoxy-based plasticizers such as sulfonamides and epoxidized soybean oil. Preferred plasticizers are organic ester plasticizers and polyalkylene oxides, with organic ester plasticizers being preferred. Plasticizers may be used singly or in combination of two or more. When using two or more, it is also preferable to use an organic ester plasticizer and a polyalkylene oxide in combination.

[0044] 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.

[0045] Examples of the polybasic organic acid ester include ester compounds of polybasic organic acids with alcohols having a linear or branched structure and 4 to 8 carbon atoms. Examples of the polybasic organic acids include adipic acid, sebacic acid, and azelaic 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, and diethylene glycol di-2-ethylbutylene. Examples of suitable organic ester plasticizers include ethylene glycol 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, 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 these may also be used. Adipic acid esters other than the above-mentioned adipic acid esters may also be used.

[0046] The organic ester plasticizer is preferably a diester plasticizer represented by the following formula (1) or (2): 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. 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 among these, an unsaturated aliphatic hydrocarbon group is more preferable. R6 may be linear or may have a branched or cyclic structure, and preferably has a cyclic structure.

[0047] From the viewpoint of reducing the viscosity of the composition, the molecular weight of the organic ester plasticizer is preferably less than 1,000, more preferably less than 500, and preferably at least 50, more preferably at least 100. 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 with a mass spectrometer (GC-MS or LC-MS).

[0048] Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.

[0049] The polyalkylene oxide used as a plasticizer is a polyalkylene oxide having no hydrolyzable silyl group. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer, and polypropylene oxide-polybutylene oxide copolymer, with polypropylene oxide being preferred.

[0050] The number average molecular weight of the polypropylene oxide used as a plasticizer is preferably 500 or more, more preferably 1,000 or more. When the number average molecular weight is equal to or greater than these lower limits, the difference in viscosity with the organic polymer (A) can be reduced, making it easier to mix with the organic polymer (A). The number average molecular weight of the polypropylene oxide used as a plasticizer is preferably 10,000 or less, more preferably 5,000 or less. When the number average molecular weight is equal to or less than these upper limits, the two-component curing thermally conductive composition is sufficiently plasticized, making it easier for the cured product to have excellent flexibility.

[0051] The plasticizer is preferably selected from triethylene glycol di-2-ethylhexanoate (3GO), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), diisononyl adipate (DINA), triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylpropanoate, and polyalkylene oxide, and more preferably selected from triethylene glycol di-2-ethylhexanoate (3GO), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), and polypropylene oxide.

[0052] The content of the plasticizer in the two-component curing thermally conductive composition is, for example, 10 parts by mass or more and 350 parts by mass or less, preferably 50 parts by mass or more and 300 parts by mass or less, more preferably 70 parts by mass or more and 240 parts by mass or less, and even more preferably 80 parts by mass or more and 180 parts by mass or less, relative to 100 parts by mass of the organic polymer (A). When the amount of the plasticizer is equal to or greater than these lower limits, flexibility and elongation are improved, and workability is also improved. When the amount of the plasticizer is equal to or less than these upper limits, curability and adhesive strength are easily ensured.

[0053] When polyalkylene oxide is used as the plasticizer, the content of the plasticizer in the two-component curing thermally conductive composition should be relatively high. Among the above, 100 parts by mass to 350 parts by mass is preferred, and 150 parts by mass to 300 parts by mass is more preferred. When polyalkylene oxide is used as the plasticizer, it is also preferred to use a combination of polyalkylene oxide and organic ester plasticizer. In this case, the mass ratio of the organic ester plasticizer content to the polyalkylene oxide content in the two-component curing thermally conductive composition is, for example, preferably 0.1 to 5, more preferably 0.2 to 2, and even more preferably 0.3 to 1.5. Furthermore, when an organic ester plasticizer is used alone as the plasticizer, the content of the organic ester plasticizer is, for example, 10 parts by mass to 240 parts by mass, preferably 50 parts by mass to 180 parts by mass, and more preferably 80 parts by mass to 150 parts by mass per 100 parts by mass of the organic polymer (A).

[0054] The plasticizer may be contained in either the first or second agent, but is preferably contained in at least the second agent, and more preferably in both the first and second agents. As described above, the second agent is substantially free of organic polymer (A). However, the inclusion of a plasticizer improves the handleability of the second agent and also facilitates dispersion of the thermally conductive filler in the second agent. The plasticizer content in the second agent is preferably 2% by mass or more and 25% by mass or less, more preferably 4% by mass or more and 20% by mass or less, and even more preferably 4.5% by mass or more and 18% by mass or less, based on the total amount of the second agent. The plasticizer may also be contained in the first agent. In this case, the plasticizer content in the first agent is preferably 2% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and even more preferably 4% by mass or more and 10% by mass or less, based on the total amount of the first agent. The plasticizer content in the first agent is preferably lower than the plasticizer content in the second agent.

[0055] <Silanol Condensation Catalyst> The two-component curing thermally conductive composition of the present invention preferably contains a silanol condensation catalyst. By containing a silanol condensation catalyst, curing of the organic polymer (A) can proceed more easily. 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.

[0056] The content of the silanol condensation catalyst in the two-component curing thermally conductive composition is preferably 0.5 parts by mass to 10 parts by mass, and more preferably 1 part by mass to 7 parts by mass, per 100 parts by mass of the organic polymer (A). 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 storage stability can be suppressed.

[0057] The silanol condensation catalyst may be contained in the second part, but not in the first part. Since water and the organic polymer (A) are substantially not contained in the second part, but are contained in the first part, this configuration can prevent the condensation reaction of the organic polymer (A) from being promoted by the silanol condensation catalyst during storage, thereby improving storage stability. Meanwhile, by mixing the silanol condensation catalyst with the first part containing the organic polymer (A) and water during use, the condensation reaction can be promoted appropriately, making it easier to improve various performances of the cured product.

[0058] <Dehydrating Agent> The two-component curing thermally conductive composition of the present invention may contain a dehydrating agent. The dehydrating agent may be contained in the second part. By including the dehydrating agent in the second part, it is possible to suppress the progression of reactions in the second part due to moisture contained in the air or the like during storage. On the other hand, the first part does not necessarily contain a dehydrating agent. Examples of dehydrating agents include silane compounds other than aminosilanes, such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane, and ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These dehydrating agents may be used alone or in combination. Among these, silane compounds other than aminosilanes are preferred, and vinylalkoxysilanes such as vinyltrimethoxysilane are more preferred.

[0059] The content of the dehydrating agent in the second part is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the first part. If the content of the dehydrating agent is equal to or greater than these lower limits, it becomes easier to suppress the occurrence of a reaction in the second part during storage. Furthermore, if the content of the dehydrating agent is equal to or less than these upper limits, it becomes possible to prevent a decrease in curability due to the dehydrating agent.

[0060] <Dispersant> The two-component curing thermally conductive composition of the present invention may contain a dispersant. The inclusion of a dispersant facilitates dispersion of the thermally conductive filler in the first part, the second part, or the two-component curing thermally conductive composition, thereby facilitating an increase in the loading rate of the thermally conductive filler. Examples of dispersants include polymeric dispersants. Examples of polymeric dispersants include polymeric compounds having functional groups. Examples of polymeric compounds include acrylic, vinyl, polyester, polyurethane, polyether, epoxy, polystyrene, amino, and silicone compounds. Examples of functional groups include carboxyl groups, phosphate groups, sulfonic acid groups, carboxylate ester groups, phosphate ester groups, sulfonate ester groups, hydroxyl groups, amino groups, quaternary ammonium bases, and amide groups. In the case of a two-component curing composition, the dispersant may be contained in either the first or second part, whichever contains the thermally conductive filler. Therefore, the dispersant may be contained in either the first or second part. The dispersant may be contained in both the first and second parts, but it is preferably contained in at least the second part.

[0061] When the second agent contains a dispersant, the content of the dispersant in the second agent is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the second agent. When the first agent contains a dispersant, the content of the dispersant in the first agent may also be the same as above, based on the total amount of the first agent.

[0062] <Thixotropy-imparting agent> The two-component curing thermally conductive composition may contain a thixotropy-imparting agent. By including a thixotropy-imparting agent in the two-component curing thermally conductive composition, thixotropy is imparted to the two-component curing thermally conductive composition, the first part, or the second part, which increases viscosity when stationary and decreases viscosity when shear is applied, improving handleability. Among the above-mentioned thixotropy-imparting agents, calcium carbonate particles, amide, fumed silica, glass fiber, etc. are mentioned, with amide being preferred. As the amide, amide wax or the like may be used. The thixotropy-imparting agent may be contained in either the first part or the second part, and may be contained in both the first part and the second part, but is preferably contained in at least the second part. By including a thixotropy-imparting agent in the second part, handleability is easily improved even if the second part does not substantially contain an organic polymer having a hydrolyzable silyl group. When the second agent contains a thixotropy-imparting agent, the content of the thixotropy-imparting agent in the second agent is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the second agent. Even when the first agent contains a thixotropy-imparting agent, the content of the dispersant in the first agent may be the same as above, based on the total amount of the first agent.

[0063] <Other Additives> The two-component curing thermally conductive composition may contain additives other than those described above. Examples of such additives include a reaction rate control agent that suppresses the reaction of the organic polymer (A), a flame retardant, an antioxidant, an ultraviolet absorber, a pigment, an anti-settling agent, a colorant such as a dye, and a compatibilizer. Examples of compatibilizers include lower alcohols such as butyl carbitol, ethanol, and isopropanol. Each additive may be contained in either the first part or the second part.

[0064] The two-component curing thermally conductive composition preferably cures by mixing and leaving at room temperature (25°C), but may also cure by heating after mixing. When curing by heating, the two-component curing thermally conductive composition may be heated to, for example, about 50 to 300°C. In addition, in a two-component two-component curing thermally conductive composition, it is preferable that both the first and second components are liquid at room temperature (25°C) from the viewpoint of ease of handling.

[0065] (Volume ratio of first agent to second agent) When obtaining a two-component curing thermally conductive composition, 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 0.67 to 1.5, 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.

[0066] (Storage Form) The first agent and the second agent are filled in separate containers, specifically, the first agent is filled in the first container and the second agent is filled in the second container. The first container and the second container may be separate or integrated. By integrating the first container and the second container, it becomes easier to supply them to the consumer as a container set. Note that in this specification, the first container filled with the first agent and the second container filled with the second agent may be collectively referred to as a container set.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] (Shear Breaking Elongation and Shear Breaking Strength) The two-component curing thermally conductive composition is preferably prepared by mixing the first and second components and leaving the mixture at 25°C for one week, and the shear breaking elongation of a 0.5 mm thick cured product is preferably 0.2 mm or more. When the shear breaking elongation is 0.2 mm or more, the flexibility of the cured product is increased and the ability to follow the thermal expansion of LiB is improved. The shear breaking elongation of a 0.5 mm thick cured product is more preferably 0.4 mm or more, even more preferably 0.5 mm or more, and even more preferably 0.6 mm or more. The shear breaking elongation of a 0.5 mm thick cured product is not particularly limited, but may be, for example, 3 mm or less, or 2 mm or less, in order to provide the cured product with appropriate mechanical strength.

[0072] The two-component curing thermally conductive composition is preferably prepared by mixing the first and second components and leaving the mixture at 25°C for one week to produce a 2mm-thick cured product having a shear break elongation of 0.45mm or more. If the shear break elongation at 2mm thickness is 0.45mm or more, the cured product will be flexible even when thick, and will have good compliance with the thermal expansion of LiB. The shear break elongation of the 2mm-thick cured product is more preferably 1mm or more, even more preferably 1.8mm or more, and even more preferably 2mm or more. The shear break elongation of the 2mm-thick cured product is not particularly limited, but may be, for example, 8mm or less or 5mm or less in order to provide the cured product with appropriate mechanical strength.

[0073] The two-component curing thermally conductive composition is prepared by mixing the first and second components and leaving the mixture at 25°C for one week. The shear breaking strength of the 0.5 mm thick cured product obtained is, for example, 0.05 MPa or more, preferably 0.2 MPa or more, more preferably 0.4 MPa or more, and even more preferably 0.55 MPa or more. If the shear breaking strength of the 0.5 mm thick cured product is above a certain level, the mechanical strength will be high even if the thickness is small, making it suitable for use as an adhesive for bonding components. The shear breaking strength of the 0.5 mm thick cured product is not particularly limited, but may be, for example, 5 MPa or less or 3 MPa or less in order to provide the cured product with appropriate flexibility.

[0074] The two-component curing thermally conductive composition is prepared by mixing the first and second components and leaving the mixture at 25°C for one week. The shear breaking strength of the 2 mm thick cured product of the two-component curing thermally conductive composition is, for example, 0.05 MPa or more, preferably 0.2 MPa or more, more preferably 0.4 MPa or more, and even more preferably 0.5 MPa or more. If the shear breaking strength of the 2 mm thick cured product is above a certain level, the mechanical strength is high, and the composition can be suitably used as an adhesive for bonding components even if the thickness is relatively large. The shear breaking strength of the 2 mm thick cured product is not particularly limited, but may be, for example, 5 MPa or less or 3 MPa or less in order to provide the cured product with appropriate flexibility.

[0075] As described below, the two-component curing thermally conductive composition of the present invention may be dehydrated by heating the second part. However, even if the composition is dehydrated by heating, it is preferable that the physical properties are not deteriorated or are only slightly deteriorated. Specifically, the ratio (heated / unheated) of the shear break elongation of the cured product of the two-component curing thermally conductive composition obtained by dehydrating the composition without heating at 25°C to the shear break elongation of the cured product of the two-component curing thermally conductive composition obtained by dehydrating the composition with heating at 100°C is preferably 80% or more, more preferably 90% or more, and even more preferably 100% or more. Furthermore, the ratio may be, for example, 200% or less, but is preferably 150% or less, and more preferably 140% or less. The shear break elongation of the cured product referred to here is the shear break elongation of a 0.5 mm thick cured product of the two-component curing thermally conductive composition obtained by mixing the first and second parts and leaving it at 25°C for one week. The details of the methods for measuring the shear breaking elongation and shear breaking strength are as described in the Examples.

[0076] (Viscosity) In the present invention, the first and second agents are preferably liquid at room temperature (25°C) from the viewpoint of ease of handling. －１ The viscosity at 25°C is preferably 10 Pa·s or more and 2500 Pa·s or less, more preferably 50 Pa·s or more and 1500 Pa·s or less, and even more preferably 100 Pa·s or more and 1000 Pa·s or less. －１When the viscosity at 25°C is within the above range, the coating property is good. －１ The viscosity at 25°C is preferably 10 Pa·s or more and 2500 Pa·s or less, more preferably 50 Pa·s or more and 1500 Pa·s or less, and even more preferably 100 Pa·s or more and 1000 Pa·s or less. －１ When the viscosity at 25°C is within the above range, the coating properties are good.

[0077] The zero shear viscosity of the first agent at 25°C is 1.0 x 10 ４ Pa・s or more 1.0×10 ７ Pa s or less is preferable, and 2.0 × 10 ４ Pa・s or more 5×10 ６ Pa s or less is more preferable, and 4.0 × 10 ４ Pa・s or more 3×10 ６ The zero shear viscosity of the second part at 25°C is preferably 1.0 x 10 Pa·s or less. When the zero shear viscosity is within the above range, the coating property is improved and dripping and the like can be prevented. ４ Pa・s or more 1.0×10 ７ Pa s or less is preferable, and 2.0 × 10 ４ Pa・s or more 5×10 ６ Pa s or less is more preferable, and 4.0 × 10 ４ Pa・s or more 3×10 ６ When the zero shear viscosity is within the above range, the application properties can be improved while preventing dripping and the like.

[0078] From the viewpoint of storage stability, it is preferable that the second agent has a low viscosity increase rate when stored at 50°C for 3 days. The viscosity increase rate of the second agent when stored at 50°C for 3 days may be, for example, 190% or less, preferably 160% or less, more preferably 145% or less, and even more preferably 135% or less. In the present invention, the viscosity increase rate can be reduced by specifying the composition of the second agent as described above. Furthermore, the viscosity increase rate can be further reduced by thermal dehydration. From the viewpoint of storage stability, the viscosity increase rate is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The viscosity increase rate is the ratio of the viscosity after heated storage at 50°C for 3 days to the viscosity (initial viscosity) before storage at 50°C for 3 days, expressed as a percentage. The viscosity is 3.16S －１ , is the viscosity measured at 25°C.

[0079] (Thermal Conductivity) The liquid curing thermally conductive composition of the present invention preferably has a thermal conductivity of 1.0 W / m·K or more, preferably 1.5 W / m·K or more, more preferably 1.8 W / m·K or more, and even more preferably 2.5 W / m·K or more. When the thermal conductivity is equal to or greater than the above lower limit, it can be said that the thermal conductivity is excellent. The higher the thermal conductivity, the better, but in practical terms, it is, for example, 50 W / m·K or less, preferably 20 W / m·K or less. The thermal conductivity can be measured by the measurement method described in the examples.

[0080] [Method for producing two-component curing thermally conductive composition] The two-component curing thermally conductive composition of the present invention can be produced, for example, by a production method comprising the following steps A and B. Step A: A step of preparing a first part containing an organic polymer (A) and water and substantially free of aminosilane. Step B: A step of preparing a second part containing an aminosilane, substantially free of water, and substantially free of organic polymer (A).

[0081] (Step A) Step A is not particularly limited as long as it can produce the first agent described above. It can be obtained by mixing the organic polymer (A) with water, and optionally a thermally conductive filler, a plasticizer, a thixotropic agent, a dispersant, and other additives. While a trace amount of aminosilane may be added to the first agent, it is preferable that no aminosilane is added and the first agent does not contain aminosilane. Here, step A is preferably performed without heating. By performing step A without heating, the organic polymer (A) and a thermally conductive filler such as aluminum hydroxide are not heated in their coexistence. This prevents side reactions that occur when the organic polymer (A) and the thermally conductive filler coexist, making it easier to improve various physical properties such as elongation and flexibility. Note that performing step A without heating means that the components constituting the first agent are not heated during the process of mixing them to obtain the first agent. For example, the temperature of the mixture may be maintained below 50°C, preferably between 0°C and 35°C. In this step A and the step B described below, the method for mixing the components is not particularly limited, and may be carried out using a known mixer such as a stirrer or kneader.

[0082] (Step B) Step B is not particularly limited as long as it can produce a second agent. It can be obtained by mixing an aminosilane and, optionally, a thermally conductive filler, a plasticizer, a silanol condensation catalyst, a dehydrating agent, a thixotropic agent, a dispersant, and other additives. Furthermore, a dehydration step is preferably performed in Step B. Dehydration may be performed on a mixture obtained by mixing all of the components constituting the second agent, but it is preferable to perform it on a mixture obtained by mixing only some of the components constituting the second agent (hereinafter also referred to as the "pre-composition"). Since dehydration generally involves heating, side reactions may occur if it is performed in a state where highly reactive components are included. However, by dehydrating the pre-composition before the highly reactive components are mixed, side reactions can be prevented. Furthermore, evaporation of relatively volatile components such as aminosilanes and dehydrating agents during dehydration can also be prevented.

[0083] When dehydration is performed, step B preferably includes the following steps B1, B2, and B3: Step B1: preparing a pre-composition that is substantially free of water and organic polymer (A) and that contains a thermally conductive filler and a plasticizer; Step B2: dehydrating the pre-composition; Step B3: adding aminosilane to the dehydrated pre-composition. By performing step B using the above steps B1 to B3, the thermally conductive filler and plasticizer that constitute the main components of the second agent, which are prone to moisture contamination, can be appropriately dehydrated, while preventing heating in a state where a highly reactive component (aminosilane) has been added. This makes it possible to prepare a second agent with a low moisture content while suppressing the production of by-products.

[0084] Step B1 is not particularly limited as long as it can produce a pre-composition containing a thermally conductive filler and a plasticizer, and can be produced by mixing the thermally conductive filler, the plasticizer, and other components (other components) that are blended as needed. The other components that can be mixed are not particularly limited as long as they do not cause or hardly cause side reactions when heated in the coexistence of the thermally conductive filler and the plasticizer, and dispersants, thixotropy-imparting agents, etc. may be appropriately mixed.

[0085] Step B2 is a step of dehydrating the pre-composition. The dehydration of the pre-composition is preferably carried out by heating. By dehydrating the pre-composition by heating, the water content of the second part can be appropriately reduced. The heating temperature during dehydration is, for example, 50°C or higher and 150°C or lower, preferably 80°C or higher and 130°C or lower, and more preferably 85°C or higher and 115°C or lower. Furthermore, from the viewpoint of appropriately reducing the water content, the pre-composition is preferably dehydrated under reduced pressure, and more preferably dehydrated by heating at the above-mentioned heating temperature while being depressurized. The pressure during depressurization may be less than 0.1 MPa in absolute pressure, but is preferably 0.05 MPa or lower, more preferably 0.03 MPa or lower, and even more preferably 0.02 MPa or lower. The lower limit of the absolute pressure during depressurization is not particularly limited, and is 0 MPa. Furthermore, the dehydration by heating may be carried out for, for example, about 0.5 to 5 hours, preferably 1 to 3 hours. The dehydration in step B2 may be carried out by a known method, for example, while mixing the pre-composition in a mixer.

[0086] Step B3 is a step in which components contained in the second part, such as aminosilane, that were not blended in step B1, are added to the pre-composition. As described above, the components added to the pre-composition in step B3 include components that undergo side reactions when added to the pre-composition and heated. In addition to aminosilane, at least one of a dehydrating agent and a silanol condensation catalyst may be added. Dispersants, thixotropy-imparting agents, etc. may also be added. Dispersants, thixotropy-imparting agents, etc. may rarely cause side reactions when added to the pre-composition and heated, but since they hardly incorporate moisture, they do not significantly increase the moisture content of the second part, even without a dehydration step. In step B3, as described above, the aminosilane and other components are added as appropriate, and then further mixed in a mixer to obtain the second part. Step B3 is preferably performed without heating, and therefore, heating is not required during the process of mixing components such as aminosilane with the pre-composition to obtain the second part, and for example, the temperature of the mixture is preferably maintained below 50° C., and preferably maintained at about 0° C. or higher and 35° C. or lower. The first part and second part obtained as described above may be filled into first and second containers, respectively, by a known method.

[0087] [Thermal Conductive Member] The thermal conductive member of the present invention includes a cured product of a two-component curing thermal conductive composition, and may be made of a cured product of the two-component curing thermal conductive composition. The thermal conductive member can be obtained by mixing a first part and a second part and curing them to form a cured product. The thermal conductive member may be used by being 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 or a cooling member, such as a heat sink or a cooling plate.

[0088] [Applications] The two-component curing 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 further, can 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, in a preferred embodiment of the present invention, a battery assembly including the above-described thermally conductive member is provided. Note that battery assemblies such as LiB assemblies can be preferably used in automobiles such as electric vehicles.

[0089] In battery assembly applications, the 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 two-component curing thermally conductive composition and thermally conductive member of the present invention are preferably used in a battery module, 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] The gap material 13 can be formed in the battery module 10 by applying a mixture of the first and second components (a two-component curing thermally conductive composition) using a common dispenser and then curing the mixture. The two-component curing thermally conductive composition is easy to store, and if mixed immediately before use, it is less likely to harden during application with the dispenser and can be quickly cured after application. Application with a dispenser is also preferable because it allows the composition to be filled relatively deep inside the housing 12 of the battery module 10.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] In this example, the evaluation was carried out by the following method. <Measurement of moisture content> The moisture content of the second part was measured by volumetric titration using a Karl Fischer moisture meter. However, the moisture content was measured for the pre-composition after dehydration. Note that the moisture content of the pre-composition after dehydration is roughly the same as the moisture content of the second part.

[0102] <Shear Test> A shear test was performed in accordance with DIN EN 1465 using the first and second parts obtained in each Example and Comparative Example. 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. The first and second parts were mixed using a static mixer to obtain a two-component curing thermally conductive composition. The two-component curing thermally conductive composition was then applied to the longitudinal edge of one of the substrates over a length of 15 mm across the entire width of the substrate, resulting in a thickness of 0.5 mm or 2 mm after curing. The longitudinal edge of the other substrate was then placed on top of the applied two-component curing thermally conductive composition, and the two-component curing thermally conductive composition was left in this state for one week in an environment of 25°C and 50% RH, thereby curing the two-component curing thermally conductive composition and obtaining a measurement sample. The obtained measurement samples were subjected to a tensile test in which the measurement samples were pulled in the longitudinal direction at a tensile speed of 10 mm / min in an environment of 25°C and 50% RH until fracture, and the strength and elongation at fracture were measured. In addition, the test specimens were observed after the shear test to observe the fracture morphology of the cured product. Two samples were prepared and each measurement value was calculated as an average of n = 2. Regarding the fracture morphology of the cured product, K indicates interfacial failure, G indicates cohesive failure, and KG indicates both interfacial failure and cohesive failure occurred. K-KG indicates that both interfacial failure and cohesive failure occurred, with interfacial failure being dominant. The tensile shear test was performed using an Instron "68TM-30" and elongation was measured using a camera (Instron "AVE 2").

[0103] <Viscosity Measurement> (Initial Viscosity) The viscosity of the first and second parts obtained in each Example and Comparative Example was measured using an Anton Paar MCR-302e rheometer while continuously changing the shear rate. Using a 25 mm diameter parallel plate at 25°C, the viscosity (Pa s) was measured at shear rates of 0.00252 (1 / s) and 3.16 (1 / s). The viscosity at a shear rate of 0.00252 (1 / s) was defined as the zero shear viscosity. Viscosity measurements were performed immediately after preparing the first and second parts. (Viscosity after Storage) The first and second parts of each Example and Comparative Example were filled into containers and stored at 50°C for 3 days, after which the viscosity (Pa s) was measured at shear rates of 0.00252 (1 / s) and 3.16 (1 / s) using the same method for measuring initial viscosity as described above. (Thickening Rate) The thickening rate was calculated from the initial viscosity and the viscosity after storage measured at a shear rate of 3.16 (1 / s) using the following formula. The closer the viscosity change rate is to 100%, the better the storage stability is. Thickening Rate (%) = 100 × Viscosity after storage / Initial viscosity

[0104] <Thermal Conductivity> The thermal conductivity of the cured product of the two-component curing thermally conductive composition of each Example and Comparative Example was determined by measuring thermal resistance using a measuring device conforming to ASTM D5470-06. Specifically, cured products of 1.0 mm, 1.5 mm, and 2.0 mm in thickness were prepared, and the thermal resistance and thickness were measured when compressed at a pressure of 30 psi. For these three thermal resistance values, a graph was created with thickness on the horizontal axis and thermal resistance on the vertical axis, and an approximate line between three points was obtained using the least squares method. The slope of the approximate line represents the thermal conductivity. Thermal resistance measurements were performed at 80°C using an LW-9389 thermometer manufactured by Long Win Science and Technology Corporation. The cured product used for the measurements was obtained by mixing the first and second parts and leaving the mixture at room temperature (25°C) for 96 hours.

[0105] In the examples and comparative examples, the following components were used: <Organic polymer (A)> "MS polymer S327" manufactured by Kaneka Corporation, number average molecular weight 25,000, linear type, terminal silylation rate 70%, specific gravity 1 g / cm ３, an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide, manufactured by Kaneka Corporation, product name "MS Polymer S203H", number average molecular weight 21,000, linear type, terminal silylation rate 60%, specific gravity 1 g / cm ３ , an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide, manufactured by Kaneka Corporation, trade name "Silyl SAT350", number average molecular weight 12,500, linear type, terminal silylation rate 91%, an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide; Kaneka Corporation "MS Polymer SAX010", number average molecular weight 5,000, linear type, terminal silylation rate 94%, an organic polymer having dimethoxymethylsilyl groups at both ends of polypropylene oxide

[0106] <Plasticizer> DINCH: diisononyl 1,2-cyclohexanedicarboxylate, specific gravity 0.97 g / cm ３ 3GO: Triethylene glycol di(2-ethylhexanoate) 3GO PPG: Polypropylene glycol, number average molecular weight: 3,000

[0107] <Aluminum hydroxide> Aluminum hydroxide 1: average particle size 1 μm, specific gravity 2.4 g / cm ３ Aluminum hydroxide 2: average particle size 10 μm, specific gravity 2.4 g / cm ３ Aluminum hydroxide 3: average particle size 105 μm, specific gravity 2.4 g / cm ３ <Aluminum oxide> Alumina 1: average particle size 0.5 μm, specific gravity 3.94 g / cm ３ ・Alumina 2: average particle size 12.5 μm, specific gravity 3.94 g / cm ３ ・Alumina 3: average particle size 71.6 μm, specific gravity 3.94 g / cm ３

[0108] <Aminosilane> - Trade name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane <Dehydrating agent> Vinylsilane, trade name "KBM-1003", manufactured by Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane <Catalyst> Silanol condensation catalyst, dibutyltin dilaurate <Thixotropy imparting agent> Trade name "T-1800", manufactured by Ito Oil Mills, Ltd., amide wax <Dispersant> BYK-Chemie "DISPERBYK-106"

[0109] Example 1: According to the formulation of the first part in Table 1, an organic polymer (A), a plasticizer, a thermally conductive filler, and water were mixed at room temperature to obtain a first part. Furthermore, according to the formulation of the second part in Table 1, the plasticizer and the thermally conductive filler were mixed at room temperature in a planetary mixer to prepare a pre-composition. The pre-composition was dehydrated by heating at 100°C for 60 minutes while stirring in the planetary mixer and reducing the pressure to 0.02 MPa. Components not contained in the pre-composition, specifically, an aminosilane, a dehydrating agent, a silanol condensation catalyst, a thixotropic agent, and a dispersant, were further added to the dehydrated pre-composition and mixed to obtain a second part. The first and second parts were each filled into a 50 cc dual cartridge. The first and second parts were each liquid. Using the obtained first and second parts, shear tests, viscosity measurements, and thermal conductivity measurements were performed according to the methods described above. The shear breaking elongation of a 0.5 mm thick cured product measured in Example 1 was calculated as the ratio (heated / unheated) to the shear breaking elongation of a 0.5 mm thick cured product measured in Example 2, which was the same except that dehydration was performed without heating (25°C) instead of heating (100°C), and this was taken as the elongation retention rate %. The shear breaking elongation of a 2 mm thick cured product was calculated in the same manner.

[0110] [Example 2] The same procedure as in Example 1 was carried out, except that the dehydration when obtaining the second agent was carried out in an environment of 25°C without heating.

[0111] Examples 3, 5, 7, 9, 11, and 13 were carried out in the same manner as in Example 1, except that the formulations of the first and second parts were changed as shown in Tables 1 to 3. The shear breaking elongation of the 0.5 mm thick cured products measured in Examples 3, 5, 7, 9, 11, and 13 was calculated as the ratio (heated / unheated) of the shear breaking elongation of the 0.5 mm thick cured products measured in the same Examples 4, 6, 8, 10, 12, and 14, except that the dehydration conditions were changed from heated (100°C) to unheated (25°C), and this was calculated as the elongation retention rate %. The shear breaking elongation of the 2 mm thick cured products was also calculated in the same manner.

[0112] Examples 4, 6, 8, 10, 12, and 14 were carried out in the same manner as in Examples 3, 5, 7, 9, 11, and 13, respectively, except that the dehydration to obtain the second agent was carried out in a 25° C. environment without heating.

[0113] Comparative Examples 1, 3, 5, 7, 9, 11, and 13 were carried out in the same manner as in Example 1, except that the formulations of the first and second parts were changed as shown in Tables 4 to 6, and that in the preparation of the second part, a pre-composition was prepared by mixing the organic polymer (A), the plasticizer, and the thermally conductive filler. The shear break elongation of the 0.5 mm-thick cured product measured in each of Comparative Examples 1, 3, 5, 7, 9, 11, and 13 was calculated as the ratio (heated / unheated) of the shear break elongation of the 0.5 mm-thick cured product measured in the same Comparative Examples 2, 4, 6, 8, 10, 12, and 14, except that the dehydration conditions were changed from heated (100°C) to unheated (25°C). The shear break elongation of the 2 mm-thick cured product was calculated in the same manner.

[0114] Comparative Examples 2, 4, 6, 8, 10, 12, and 14 were carried out in the same manner as in Comparative Examples 1, 3, 5, 7, 9, 11, and 13, respectively, except that dehydration when obtaining the second agent was carried out in an environment of 25° C. without heating. Note that Comparative Examples 1 to 14 are each a comparative example for the purpose of roughly comparing with Examples 1 to 14, respectively.

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] *In Tables 1 to 6, the results of each Example and Comparative Example are shown in the column for second part. *The column for composition shows the composition of the two-component curing thermally conductive composition after mixing the first and second parts.

[0121] As is clear from the above results, in each Example, the first part contained organic polymer (A) and water but was substantially free of aminosilane, while the second part contained aminosilane but was substantially free of water and organic polymer (A). This resulted in no significant increase in viscosity even when heated at 50°C for 3 days, and good storage stability. Furthermore, in each Example, flexibility was good, and even when heated for dehydration during production, the elongation retention rate was high, preventing a deterioration in flexibility. In contrast, in the Comparative Example, not only the first part but also the second part contained organic polymer (A). Therefore, viscosity was likely to increase if dehydration was not performed during production, and heating for dehydration during production reduced the elongation retention rate and impaired flexibility.

[0122] DESCRIPTION OF SYMBOLS 10 Battery module 11, 21 Battery cell 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

1. A two-component curing thermally conductive composition comprising an organic polymer having a hydrolyzable silyl group, a thermally conductive filler, an aminosilane, and water, the two-component curing thermally conductive composition comprising: a first part containing the organic polymer and the water but substantially free of the aminosilane, the first part being filled in a first container; and a second part containing the aminosilane, substantially free of water, and substantially free of the organic polymer, the second part being filled in a second container.

2. The two-component curing thermally conductive composition according to claim 1, wherein the first part and the second part are mixed, left to stand at 25°C for one week, and the shear breaking elongation of a 0.5 mm thick cured product is 0.2 mm or more.

3. The two-component curable thermally conductive composition according to claim 1 or 2, wherein the organic polymer has a number average molecular weight of 1,000 or more.

4. The two-component curing thermally conductive composition according to claim 1 or 2, wherein the content of the thermally conductive filler is 300 parts by mass or more and 3,000 parts by mass or less per 100 parts by mass of the total of the organic polymer and plasticizer contained in the two-component curing thermally conductive composition.

5. A two-component curable thermally conductive composition according to claim 1 or 2, wherein both the first and second components contain the thermally conductive filler.

6. The two-component curable thermally conductive composition according to claim 1 or 2, wherein the viscosity increase rate of the second part when stored at 50°C for 3 days is 190% or less.

7. The two-component curable thermally conductive composition according to claim 1 or 2, wherein the second part contains a plasticizer.

8. The two-component curable thermally conductive composition according to claim 1 or 2, wherein the second part contains a silanol condensation catalyst.

9. A thermally conductive member comprising a cured product of the two-component curing thermally conductive composition according to claim 1 or 2.

10. A battery assembly comprising the thermally conductive member according to claim 9.

11. A method for producing a two-component curing thermally conductive composition containing an organic polymer having a hydrolyzable silyl group, a thermally conductive filler, an aminosilane, and water, comprising the steps of: preparing a first part containing the organic polymer and the water and substantially not containing the aminosilane; and preparing a second part containing the aminosilane, substantially not containing water, and substantially not containing the organic polymer.

12. The method for producing a two-component curing thermally conductive composition according to claim 11, wherein the step of preparing the second part comprises the steps of: preparing a pre-composition that is substantially free of water and the organic polymer, and that contains the thermally conductive filler and a plasticizer; dehydrating the pre-composition; and adding an aminosilane to the pre-composition after dehydration.

13. The method for producing a two-component curable thermally conductive composition according to claim 12, wherein the pre-composition is dehydrated by heating.

Images