Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a thermally conductive composition.
• Thermal conductive compositions containing thermally conductive fillers are widely known as curable liquids. 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 material such as a heat dissipating gap filler that transfers heat generated by the heat generating element to the heat sink.
• lithium-ion batteries LiBs
• thermally conductive compositions are often filled between components in lithium-ion batteries, such as battery cells, battery modules, and battery packs, to secure the components together and improve heat dissipation.
• Patent Document 1 discloses an invention relating to a thermally conductive curable composition comprising a first part and a second part. It discloses that the first part comprises a catalyst, a ceramic filler mixture, a low-volatility organic liquid, and water, while the second part comprises a silyl-modified reactive polymer, a low-volatility organic liquid, and a ceramic filler. Furthermore, paragraph 0038 discloses that the viscosity of the first part is greater than approximately 300 Pa ⁇ s, and the viscosity of the second part is approximately 200 to 1500 Pa ⁇ s.
• Patent Document 2 also discloses an invention related to a thermally conductive silicone potting composition
• a thermally conductive silicone potting composition comprising a first component and a second component.
• the first component comprises a vinyl organopolysiloxane, an alumina filler having an average particle size within a specific range, an aluminum hydroxide filler, and a catalyst
• the second component comprises a hydride organopolysiloxane, an alumina filler having an average particle size within a specific range, and an aluminum hydroxide filler.
• thermally conductive compositions such as those described in Patent Document 1 have high viscosity, and therefore, when such compositions are used in batteries, it is difficult to sufficiently fill gaps.
• the present invention therefore aims to provide a thermally conductive composition that has low viscosity during use, yet can prevent the thermally conductive filler from settling during storage.
• a two-component curing thermally conductive composition comprising: a first part containing at least one of a curable liquid resin and a plasticizer, and a thermally conductive filler, and having a viscosity of 90 Pa s or more and 1000 Pa s or less, and filled in a first container; and a second part containing at least one of the curable liquid resin and the plasticizer, and having a viscosity of 10 Pa s or less, and filled in a second container, wherein at least one of the first part and the second part contains the curable liquid resin, the thermally conductive filler in the first part has an average particle size of 5 ⁇ m or more, the second part does not contain a thermally conductive filler, or contains the thermally conductive filler with an average particle size of less than 5 ⁇ m, and the viscosity of the thermally conductive composition after mixing the first part and the second part is 1 Pa s or more and less than 60 Pa s.
• the organic polymer having a hydrolyzable silyl group is a polyalkylene oxide having a hydrolyzable silyl group.
• thermally conductive composition according to any one of [1] to [8], wherein the thermally conductive filler contains aluminum hydroxide.
• a method for using a two-component curing thermally conductive composition comprising: a first part containing at least one of a curable liquid resin and a plasticizer, and a thermally conductive filler, and having a viscosity of 90 Pa ⁇ s or more and 1000 Pa ⁇ s or less, and filled in a first container; and a second part containing at least one of the curable liquid resin and the plasticizer, and having a viscosity of 10 Pa ⁇ s or less, and filled in a second container, wherein at least one of the first part and the second part is the curable liquid resin.
• the thermally conductive filler in the first agent has an average particle size of 5 ⁇ m or more
• the second agent does not contain a thermally conductive filler or contains the thermally conductive filler with an average particle size of less than 5 ⁇ m
• the viscosity of the thermally conductive composition after mixing the first agent and the second agent is 1 Pa s or more and less than 60 Pa s
• the first agent and the second agent are mixed at a volume ratio of the first agent to the second agent (first agent/second agent) of 95/5 to 70/30, and then applied.
• the present invention provides a thermally conductive composition that has low viscosity during use, yet can suppress settling of the thermally conductive filler during storage.
• FIG. 2 is a schematic diagram illustrating a container set according to one embodiment.
• FIG. 10 is a schematic diagram showing a container set according to another embodiment.
• 1 is a graph showing the relationship between the mixing ratio of the first agent and the second agent and the viscosity after mixing the first agent and the second agent in Example 1.
• the thermally conductive composition of the present invention is a two-component curing thermally conductive composition comprising a first part and a second part.
• the first part contains at least one of a curable liquid resin and a plasticizer, and a thermally conductive filler, has a viscosity of 90 Pa ⁇ s or more and 1000 Pa ⁇ s or less, and is filled into a first container.
• the content of the thermally conductive filler in the thermally conductive composition is preferably 10 to 80% by volume, more preferably 20 to 75% by volume, and even more preferably 35 to 72% by volume, based on the total volume of the thermally conductive composition.
• the thermal conductivity of the thermally conductive composition is likely to be improved.
• the viscosity of the thermally conductive composition can be adjusted to a certain level or below, making it easier to fill narrow gaps inside battery modules and the like with the thermally conductive composition.
• the number-average molecular weight of the organic polymer having a hydrolyzable silyl group is above these lower limits, settling of the thermally conductive filler is more easily suppressed.
• the number-average molecular weight (Mn) refers to the number-average molecular weight (Mn) of all of them.
• the number average molecular weight of an organic polymer having a hydrolyzable silyl group 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 the solvent, a column temperature of 40°C, and a flow rate of 0.3 ml/min.
• polyalkylene oxide polymers with a polypropylene oxide main chain skeleton and dimethoxysilyl groups at the ends of the main chain skeleton include AGC Inc.'s product names "Excestar A2410,” “Excestar S4530,” and “Excestar S6250,” and Kaneka Corporation's product names "S203,” “SAT115,” and "SAX010.”
• the difference between the resin content of the first agent and the resin content of the second agent is, for example, 85% by volume or less, preferably 80% by volume or less, and more preferably 75% by volume or less, based on the total amount of each agent.
• the resin content refers to the total volume percentage of the curable liquid resin, plasticizer, and the dehydrating agent, adhesion promoter, and dispersant, which will be described later, in each agent.
• polybasic organic acid ester examples include ester compounds of a polybasic organic acid and an alcohol having a linear or branched structure and having 4 to 8 carbon atoms.
• polybasic organic acid examples include adipic acid, sebacic acid, and azelaic acid.
• organic ester plasticizer examples 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.
• the plasticizer preferably includes triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethylbutyrate (3GH), or triethylene glycol di-2-ethylpropanoate.
• the plasticizer more preferably includes triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethylbutyrate (3GH), and even more preferably includes triethylene glycol di-2-ethylhexanoate.
• the content of the catalyst in the thermally conductive composition is preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the organic polymer having a hydrolyzable silyl group.
• the content of the catalyst in at least one of the first and second parts is also preferably within this range.
• At least one of the first and second parts constituting the thermally conductive composition of the present invention preferably contains water, which is preferable because after the first and second parts are mixed to prepare the thermally conductive composition, the composition can be quickly cured to the inside.
• the water content in the thermally conductive composition is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 20 parts by mass, and even more preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of the organic polymer having a hydrolyzable silyl group.
• the water content in at least one of the first and second parts is also preferably within this range.
• the second part does not need to contain a dispersant, but it is preferable that the second part contains a dispersant.
• the dispersant acts on the thermally conductive filler contained in the first part, allowing the thermally conductive filler to be properly dispersed in the composition, making it possible to adjust the viscosity of the thermally conductive composition to a certain level or less and making it easier to fill narrow gaps inside battery modules, etc.
• the first agent may or may not contain a dispersant.
• Dispersants include polymeric dispersants.
• Polymeric dispersants include polymeric compounds with functional groups. Examples of polymeric compounds include acrylic, vinyl, polyester, polyurethane, polyether, epoxy, polystyrene, amino, and silicone compounds. Functional groups include carboxyl groups, phosphate groups, sulfonic acid groups, carboxylic acid ester groups, phosphate ester groups, sulfonic acid ester groups, hydroxyl groups, amino groups, quaternary ammonium bases, and amide groups. Dispersants other than polymeric dispersants may also be used, such as alkoxysilane compounds.
• the content of the dehydrating agent in the first or second agent is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the organic polymer having a hydrolyzable silyl group contained in the thermally conductive composition obtained by mixing the first and second agents.
• the content of the dehydrating agent is equal to or greater than these lower limits, hardening during storage is easily suppressed, and when the content of the dehydrating agent is equal to or less than these upper limits, an increase in hardness over time due to the dehydrating agent can be made less likely to occur.
• the content of the dehydrating agent in the thermally conductive composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the organic polymer having a hydrolyzable silyl group.
• the first agent, the second agent, and the thermally conductive composition obtained by mixing these may contain other additives such as antioxidants, ultraviolet absorbers, antifoaming agents, pigments, dyes, anti-settling agents, and solvents.
• the volume ratio of the first agent to the second agent is preferably 95/5 to 70/30, more preferably 95/5 to 75/25, and even more preferably 94/6 to 80/20.
• the specific gravity of the first agent is preferably 1.6 or more and 3 or less, more preferably 1.75 or more and 2.5 or less, and even more preferably 1.9 or more and 2.2 or less.
• the specific gravity of the second agent is preferably 0.3 or more and 1.8 or less, more preferably 0.5 or more and 1.5 or less, and even more preferably 0.8 or more and 1.3 or less.
• the first container filled with the first agent and the second container filled with the second agent may be separate or integrated.
• the integration of the first container and the second container facilitates supply to the consumer as a container set.
• 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.
• the first agent 35 and the second agent 36 may be ejected from each ejection port 31A, 32A after the lids 33B, 34B are removed and the first agent 35 and the second agent 36 are pushed out by pistons (not shown) inserted from the openings.
• the container set may include, as shown in FIG. 2, 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, 44B.
• the thermally conductive composition of the present invention can be used in a variety of applications.
• the composition can suppress sedimentation of the thermally conductive filler during storage of the first and second parts, while maintaining a viscosity below a certain level after mixing the first and second parts. This makes the composition particularly suitable for use as a gap filler for filling narrow gaps.
• Specific applications include, for example, gap fillers in batteries, electronic devices, semiconductor devices, etc., and the composition is preferably used in battery applications.
• gap fillers made of the thermally conductive composition are filled between battery cells, between a battery cell and a battery module case, between a battery cell and a battery pack case, between a battery cell and a cooling plate, between a battery module case and a cooling plate, or between a battery pack case and a cooling plate.
• the filled gap filler may be in close contact with the battery cell, battery module case, battery pack case, or cooling plate. This allows the gap filler between battery cells to maintain a separation between the battery cells.
• the gap material between the battery cell and the battery module case, between the battery cell and the battery pack case, or between the battery cell and the cooling plate is in close contact with both the battery cell and the battery module case, the battery pack case, or the cooling plate, and has the function of transferring heat generated in the battery cell to the battery module case, the battery pack case, or the cooling plate.
• the thermally conductive composition is used for a battery application, it is not particularly limited, but is preferably used in a two-wheeled vehicle, a three-wheeled vehicle, or an automobile, and more preferably used in a two-wheeled vehicle, a three-wheeled vehicle, or an automobile equipped with a lithium-ion battery.
• the viscosity (Pa ⁇ s) at 25° C. of each of the first part, the second part, and the thermally conductive composition obtained by mixing these parts was measured by the following method. Using a rheometer (for example, an Anton Paar rheometer "MCR-302e"), the sample temperature was adjusted to 25°C using a Peltier plate, and viscosity was measured using parallel plates with a diameter of 20 mm, with a gap of 1 mm, while continuously changing the shear rate within the range of 0.0001 to 100 (1/sec). The viscosity value was measured at a shear rate of 3.16 (1/sec).
• the viscosity difference was calculated based on the measured values of the viscosity of the first and second parts.
• the viscosity of the thermally conductive composition was measured immediately after mixing the first and second parts.
• "immediately after mixing” means measuring before a significant increase in viscosity occurs.
• the above samples i.e., the first and second parts
• the viscosity of the thermally conductive composition was measured within 10 minutes after the stirring was completed.
• thermal conductivity The thermally conductive compositions prepared in each of the examples and comparative examples were cured for two weeks in an environment of 25°C and 50% RH to obtain cured products, which were used as samples to measure thermal conductivity.
• Thermal conductivity was determined by measuring thermal resistance using a measuring device conforming to ASTM D5470-06. Specifically, cured materials with thicknesses of 1.0 mm, 1.5 mm, and 2.0 mm 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 the three points was determined using the least squares method. The slope of the approximate line was then the thermal conductivity.
• Kaneka Corporation's “MS Polymer SAX015" a number-average molecular weight of 5,000, branched type, terminal silylation rate of 95%, an organic polymer having dimethoxymethylsilyl groups at both ends of branched polypropylene oxide.
• Aluminum hydroxide 1 (average particle size 1 ⁇ m) Aluminum hydroxide 2 (average particle size 10 ⁇ m) Aluminum hydroxide 3 (average particle size 50 ⁇ m) Aluminum hydroxide 4 (average particle size 100 ⁇ m)
• Dehydrating agent vinyltrimethoxysilane
• Adhesion promoter N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
• Silanol condensation catalyst organotin curing catalyst ("KSF-01" manufactured by Sankyo Pharmaceutical Co., Ltd.)
• Water and dispersant BYK-Chemie "DISPERBYK-145"
• Dispersant BYK-Chemie "DISPERBYK-106”
• Pigment Cyanine blue Antifoaming agent: "Floren AC-2300C” manufactured by Kyoeisha Chemical Co., Ltd.
• Antioxidant Songwon "SONGNOX1010"
• Example 1 A first part was prepared by mixing an organic polymer having a hydrolyzable silyl group (MS polymer SAT115, MS polymer SAX010), a plasticizer, aluminum hydroxides 1 to 4, water, a pigment, an antifoaming agent, and an antioxidant according to the formulation in Table 1.
• a second part was prepared by mixing a plasticizer, a dehydrating agent, an adhesion promoter, a silanol catalyst, and a dispersant according to the formulation in Table 1.
• the first and second agents prepared as described above were weighed into a 200 ml polypropylene container so that the total weight was 100 g in the volume ratio shown in Table 1, and the contents of the container were stirred for 1 minute using a 15 mm wide polypropylene spatula at a rate of 2 revolutions per second to obtain a thermally conductive composition composed of the first and second agents.
• Examples 2 to 9 Comparative Examples 1 to 4
• a thermally conductive composition composed of a first part and a second part was obtained in the same manner as in Example 1, except that the type and amount of each component was changed according to Tables 1 and 2.
• the thermally conductive compositions of the above examples all satisfied the specified requirements for the viscosity of the first and second parts, as well as the viscosity after mixing the first and second parts. Therefore, while the thermal conductivity was good, the settling of the thermally conductive filler during storage of the first and second parts was suppressed, and the thermally conductive composition obtained by mixing the first and second parts had good coatability and excellent flowability in narrow gaps. In contrast, the thermally conductive composition prepared in Comparative Example 1 had a viscosity of the second agent and a viscosity after mixing the first and second agents that both exceeded the specified standards, and good applicability could not be achieved.
• the average particle size of the thermally conductive filler contained in the second agent exceeded the specified standard, and it was not possible to suppress the settling of the thermally conductive filler in at least the second agent during storage of the first and second agents.
• the thermally conductive composition prepared in Comparative Example 4 had a viscosity of the first part that was below the specified standard, and was unable to suppress the settling of the thermally conductive filler in at least the first part during storage of the first and second parts.

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