Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/14—Solid materials, e.g. powdery or granular
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • 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 resin composition for heat-dissipating gap fillers, heat-dissipating gap fillers, and articles.
• fillers or adhesives with high thermal conductivity between constituent members As a method of efficiently dissipating heat, it is known to use fillers or adhesives with high thermal conductivity between constituent members.
• This type of filler or adhesive is called a gap filler, and is generally a material in which a metal oxide with high thermal conductivity is contained in a resin component. It has the advantage that automatic mounting is possible with a coating device called a dispenser.
• Silicone may have elastomeric properties suitable for this application, but when used near electrical contacts such as battery cells, the volatile silicone contained in it and the low-molecular-weight siloxane generated from it cause contact failure. Moreover, since it is a moisture-curing reaction, water may be added, but the generation of voids due to water leads to a decrease in thermal conductivity. In addition, problems of volume shrinkage due to volatilization of volatile silicone, low-molecular-weight siloxane and water, and problems of decreased storage stability due to separation of water from the liquid prior to curing have also been pointed out.
• Polyurethane can also exhibit excellent elastomer properties, but its raw material, isocyanate, not only has toxicity concerns, but also reacts with water to form carbon dioxide voids. Therefore, it is necessary to carry out the curing reaction in the absence of water in order not to create voids that interfere with thermal conductivity.
• heat-dissipating gap fillers need to contain inorganic fillers with a high surface area (small particle size) at a high concentration. Extensive and therefore costly drying processes and handling are required.
• Patent Document 1 "(A) a liquid epoxy resin, (B) an inorganic filler, (C) a phosphate ester-based wetting and dispersing agent, and (D) a urea-based compound as a main component, and (E) It contains a curing agent and (F) a curing agent component containing a curing accelerator, and the content of the (C) phosphate ester-based wetting and dispersing agent is 0.1 parts per 100 parts by mass of the (A) liquid epoxy resin.
• Patent Document 2 describes "A two-component curable composition that cures to form a thermally conductive cured product, comprising (i) at least one polymerizable (meth)acrylate-based monomer component (ii) a peroxide-based curing agent component; (iii) one or more co-curing components selected from the group consisting of compounds containing primary, secondary or tertiary amines or -CONHNH- groups; (iv) a stabilizing component; and (v) a first portion comprising a filler component; and (i) at least one polymerizable (meth)acrylate-based monomer component; (ii) (iii) a stabilizing component; and (iv) a thermally conductive filler component, wherein at least one portion of the composition comprises:
• the composition described in US Pat. No. 5,800,005 is suitable for bonding heat-generating components, such as electrical components, to substrates, such as radiators. described as beneficial to
• thermally conductive gap filler comprising an aziridino-functional polyether polymer and at least 30% by volume of thermally conductive filler based on the total volume of the gap filler; Thermally conductive gap fillers are said to be suitable for use in electronic applications such as battery assemblies.
• U.S. Patent No. 5,200,202 discloses a curable composition comprising a polyol component comprising one or more polyols, a functional butadiene component, and, based on the total weight of the curable composition, at least 20 a thermally conductive filler, present in a weight percent amount, wherein the curable composition has a thermal conductivity of at least 0.5 W/(mK) after curing;
• the curable compositions of US Pat. No. 6,200,000 may be used, for example, as thermally conductive gap fillers, which are said to be suitable for use in electronic applications such as battery assemblies.
• JP 2016-60826 A Japanese Patent Publication No. 2007-528437 Japanese Patent Publication No. 2020-511732 Japanese Patent Publication No. 2022-507500
• the epoxy system of Patent Document 1 at least when the curing agent is an acid anhydride, which is described in its examples, requires a long time to cure at room temperature, so curing at a high temperature is necessary.
• many liquid epoxy compounds are feared to be mutagenic.
• the acrylic of Patent Document 2 cannot be stored at a temperature higher than the decomposition temperature of the peroxide that is the curing agent, and the curing temperature must be strictly controlled in order to obtain stable performance with the cured product.
• many of the (meth)acrylate compounds have skin sensitization, and the safety of workers is a concern.
• Patent Document 3 there is concern about toxicity due to the aziridino group, and since it is generally a water-soluble resin, there is a high possibility that a large amount of water is contained in the system, which leads to the generation of voids and volumetric shrinkage.
• the present invention provides a heat dissipating gap filler resin that can reduce the occurrence of cracks and peeling even when the heat dissipating gap filler is exposed to high temperature conditions for a long time or undergoes a sudden temperature change.
• the object is to provide a composition.
• the present inventors have found that a resin composition for a heat-dissipating gap filler containing maleic anhydride-modified polybutadiene, hydroxyl-modified polybutadiene, a thermally conductive filler, and an antioxidant, wherein the oxidation
• the content of the inhibitor is 0.01% by mass or more when the total amount of the resin composition for heat dissipating gap filler is 100% by mass, and the thermal conductivity of the resin composition for heat dissipating gap filler after curing is 1.0 W/m ⁇ K or more
• the heat-dissipating gap filler resin composition will not crack even if the heat-dissipating gap filler is exposed to high temperature conditions for a long time or undergoes a sudden temperature change.
• the inventors have found that it is possible to reduce the occurrence of peeling and peeling, and completed the present invention.
• thermoelectric material composition that is, according to the present invention, the following heat-dissipating gap filler resin composition, heat-dissipating gap filler, and article are provided.
• a heat dissipating gap filler resin that can reduce the occurrence of cracks and peeling even when the heat dissipating gap filler is exposed to high temperature conditions for a long time or undergoes a sudden temperature change.
• a composition can be provided.
• the resin composition for heat-dissipating gap fillers of the present embodiment is a resin composition for heat-dissipating gap fillers containing maleic anhydride-modified polybutadiene, hydroxyl group-modified polybutadiene, a thermally conductive filler, and an antioxidant.
• the content of the antioxidant is 0.01% by mass or more when the total amount of the resin composition for the heat dissipating gap filler is 100% by mass
• the content of the resin composition for the heat dissipating gap filler after curing Thermal conductivity is 1.0 W/m ⁇ K or more.
• the thermal conductivity of the heat-dissipating gap filler resin composition of the present embodiment after curing is 1.0 W/m ⁇ K or more.
• the thermal conductivity of the heat-dissipating gap filler resin composition of the present embodiment after curing is preferably 1.5 W/m ⁇ K or more, more preferably 2.3 W/m, from the viewpoint of further improving thermal conductivity.
• ⁇ K or more more preferably 2.5 W/m ⁇ K or more, more preferably 2.7 W/m ⁇ K or more.
• the upper limit is not particularly limited, for example, it may be 10.0 W/m K or less, 8.0 W/m K or less, or 5.0 W/m K or less.
• the thermal conductivity after curing of the heat-dissipating gap filler resin composition of the present embodiment is, for example, the type and content of the thermally conductive filler, the type and content of the maleic anhydride-modified polybutadiene and the hydroxyl group-modified polybutadiene, and the like. can be made within the range of the present embodiment by adjusting The thermal conductivity after curing of the resin composition for heat-dissipating gap filler indicates a value measured by the method described in Examples.
• the Shore OO type hardness measured according to ASTM D2240 of the resin composition for a heat dissipating gap filler of the present embodiment is preferably 80 or less, from the viewpoint of further reducing cracking and peeling of the heat dissipating gap filler. It is more preferably 75 or less, still more preferably 70 or less, and although the lower limit is not particularly limited, it may be, for example, 40 or more, or 43 or more. Hardness in this specification indicates the hardness measured for a sample produced by the method described in Examples.
• the Shore O type hardness measured according to ASTM D2240 of the resin composition for the heat dissipating gap filler of the present embodiment is preferably 50 or less, from the viewpoint of further reducing cracking and peeling of the heat dissipating gap filler. It is more preferably 45 or less, still more preferably 40 or less, and although the lower limit is not particularly limited, it may be, for example, 10 or more, or 13 or more.
• the resin composition for heat-dissipating gap fillers of the present embodiment is preferably a two-component resin composition for heat-dissipating gap fillers.
• the storage stability of the resin composition for heat-dissipating gap fillers before curing is further improved when the resin composition for heat-dissipating gap fillers is a two-liquid type.
• the resin composition for heat-dissipating gap fillers of the present embodiment is a two-liquid resin composition for heat-dissipating gap fillers, liquid A containing maleic anhydride-modified polybutadiene and a thermally conductive filler, and hydroxyl-modified polybutadiene , and a B liquid containing a thermally conductive filler.
• maleic anhydride-modified polybutadiene and hydroxyl-modified polybutadiene which are the resin components thereof, are preferably not mixed during storage but mixed before use. . That is, liquid A containing maleic anhydride-modified polybutadiene and liquid B containing hydroxyl-modified polybutadiene are stored separately, mixed before use, then injected and coated, and cured to improve heat dissipation. Gap filler.
• the viscosity of liquid A is preferably 500 Pa s from the viewpoint of further improving supply stability using a pump in a coating device when applying the heat-dissipating gap filler.
• the viscosity of liquid B is preferably 500 Pa s from the viewpoint of further improving supply stability using a pump in a coating apparatus when applying the heat-dissipating gap filler.
• the viscosities of liquid A and liquid B in this specification are values measured by the method described in Examples.
• the thermal conductivity of liquid A is preferably 1.0 W/m ⁇ K or more, more preferably 1.5 W/m ⁇ K or more, from the viewpoint of further improving thermal conductivity.
• K or more more preferably 2.0 W/m ⁇ K or more, more preferably 2.5 W/m ⁇ K or more, still more preferably 2.7 W/m ⁇ K or more, still more preferably 3.0 W/m ⁇ K or more , and more preferably 3.5 W/m ⁇ K or more.
• the upper limit is not particularly limited, for example, it may be 10.0 W/m K or less, 8.0 W/m K or less, or 5.0 W/m K or less.
• the thermal conductivity of liquid B is preferably 1.0 W/m ⁇ K or more, more preferably 1.5 W/m ⁇ K or more, from the viewpoint of further improving thermal conductivity.
• K or more more preferably 2.0 W/m ⁇ K or more, more preferably 2.5 W/m ⁇ K or more, still more preferably 2.7 W/m ⁇ K or more, still more preferably 3.0 W/m ⁇ K or more , and more preferably 3.5 W/m ⁇ K or more.
• the upper limit is not particularly limited, for example, it may be 10.0 W/m K or less, 8.0 W/m K or less, or 5.0 W/m K or less. you can The thermal conductivities of liquid A and liquid B in this specification are values measured by the method described in Examples.
• the maleic anhydride-modified polybutadiene of this embodiment is produced by modifying a butadiene homopolymer with maleic anhydride. are exemplified.
• the content of the maleic anhydride-modified polybutadiene of the present embodiment is, when the total amount of the heat-dissipating gap filler resin composition of the present embodiment is 100% by mass, from the viewpoint of further improving the performance balance between handling property and sheet moldability. Therefore, it is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more, and still more preferably 1.2% by mass or more, and the viscosity is adjusted to a more appropriate From the viewpoint of the range, it is preferably 10.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 6.0% by mass or less, and even more preferably 5.5% by mass or less.
• the content of maleic anhydride-modified polybutadiene contained in liquid A is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, more preferably 2.0% by mass or more, still more preferably 2.4% by mass or more, and from the viewpoint of making the viscosity a more appropriate range Therefore, it is preferably 20.0% by mass or less, more preferably 14.0% by mass or less, still more preferably 12.0% by mass or less, and still more preferably 11.0% by mass or less.
• the hydroxyl group-modified polybutadiene of the present embodiment is obtained by hydroxylating polybutadiene, specifically Poly bd R-20LM manufactured by Clay Valley, Poly bd R-15HT and Poly bd R manufactured by Idemitsu Kosan Co., Ltd. -45HT, POLYVEST HT from Evonik, NISSO-PB G-1000, NISSO-PB G-2000, NISSO-PB G-3000 from Nippon Soda Co., Ltd., Hydroxyl-terminated Polymer Butadiene from Zibo, and the like.
• the content of the hydroxyl group-modified polybutadiene of the present embodiment is preferably 0.2% by mass from the viewpoint of further improving handling properties when the total amount of the heat-dissipating gap filler resin composition of the present embodiment is 100% by mass.
• the content of the hydroxyl group-modified polybutadiene contained in the B liquid is preferably 0.5% from the viewpoint of further improving the handling property when the total amount of the B liquid is 100% by mass. 5% by mass or more, more preferably 0.7% by mass or more, more preferably 1.0% by mass or more, and from the viewpoint of making the viscosity a more appropriate range, preferably 20.0% by mass or less, more It is preferably 14.0% by mass or less, more preferably 10.0% by mass or less, still more preferably 6.0% by mass or less, still more preferably 4.0% by mass or less, further preferably 3.6% by mass or less. .
• the contents of the maleic anhydride-modified polybutadiene of the present embodiment and the hydroxyl group-modified polybutadiene of the present embodiment are determined by the number of maleic anhydride residues in the maleic anhydride-modified polybutadiene involved in the reaction, the number of hydroxyl groups in the hydroxyl group-modified polybutadiene, and the It is determined in consideration of the physical properties of the resin to be obtained later.
• the total content of the maleic anhydride-modified polybutadiene of the present embodiment and the hydroxyl group-modified polybutadiene of the present embodiment is, for example, 0.5% when the total amount of the heat-dissipating gap filler resin composition of the present embodiment is 100% by mass.
• the total content of the maleic anhydride-modified polybutadiene of the present embodiment and the hydroxyl group-modified polybutadiene of the present embodiment is 100% by mass of the total amount of the heat-dissipating gap filler resin composition of the present embodiment. From the viewpoint of improving the % by mass or more, more preferably 3.0% by mass or more, and from the viewpoint of setting the viscosity in a more appropriate range, preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass. 10% by mass or less, and more preferably 10% by mass or less.
• thermally conductive filler Any known thermally conductive filler can be used as the thermally conductive filler of the present embodiment, but an electrically insulating thermally conductive filler is preferable when the breakthrough voltage is a concern.
• Electrically insulating and thermally conductive fillers include inorganic particles such as oxides, hydrates, nitrides, carbonates, and carbides. Hydrates such as zinc include, for example, aluminum hydroxide and magnesium hydroxide Nitrides include boron nitride and aluminum nitride Carbonates include magnesium carbonate and anhydrous magnesium carbonate Carbide includes For example, silicon carbide is preferably used. Metals such as graphite, carbon nanotubes, and aluminum can also be used if electrical insulation is not considered.
• the thermally conductive filler of this embodiment preferably contains at least one selected from the group consisting of aluminum oxide, aluminum hydroxide, aluminum nitride, zinc oxide, anhydrous magnesium carbonate, and silicon carbide.
• the content of the thermally conductive filler of the present embodiment is preferably 70% by mass or more from the viewpoint of further improving thermal conductivity when the total amount of the resin composition for a heat-dissipating gap filler of the present invention is 100% by mass. , More preferably 75% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and from the viewpoint of further improving handling properties, preferably 99% by mass or less, more preferably 97% by mass % or less, more preferably 95 mass % or less.
• the thermally conductive filler is preferably contained in each of the A liquid and the B liquid.
• the thermally conductive filler is preferably contained in each of liquids A and B, it is possible to more appropriately balance the viscosities of liquids A and B, and improve operability when mixing liquids A and B. can be improved.
• the content of the thermally conductive filler contained in liquid A is preferably 70% by mass or more, more preferably 75% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and from the viewpoint of further improving handling properties, preferably 99% by mass or less, more It is preferably 97% by mass or less, more preferably 95% by mass or less.
• the content of the thermally conductive filler contained in liquid B is preferably 70% by mass or more, more preferably 75% by mass or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and from the viewpoint of further improving handling properties, preferably 99% by mass or less, more It is preferably 97% by mass or less, more preferably 95% by mass or less.
• thermally conductive fillers can be thermally conductive by using one or more of them, by combining the same type of inorganic particles with different particle sizes, or by adjusting their content. It is possible to control the properties and viscosity of the resin composition, but while aiming to maximize thermal conductivity, the viscosity of the resin composition for exoergic gap fillers can be easily manipulated such as injection and coating. It is preferable to use a combination of inorganic particles having different particle sizes in order to control the particle size within the range that can be achieved. By carrying out like this, thermal conductivity can be improved more, adjusting to an appropriate viscosity. In the case of imparting flame retardancy, it is also possible to use hydrates, for example, by selecting aluminum hydroxide or magnesium hydroxide instead of oxides.
• the heat-dissipating gap filler Since the heat-dissipating gap filler is intended to dissipate heat, it is naturally used in places where it is exposed to high temperatures for a long period of time or where it is repeatedly exposed to high temperatures and room temperature.
• the resin composition for heat-dissipating gap fillers of the present embodiment is susceptible to thermal degradation due to heat, water, oxygen, etc., of double bonds derived from butadiene chains, and is likely to undergo a cross-linking reaction between butadiene chains.
• the heat-dissipating gap filler becomes hard and brittle, causing cracks and peeling.
• the resin composition for heat-dissipating gap fillers of the present embodiment contains an antioxidant.
• antioxidants known antioxidants can be used, and phenolic antioxidants, phosphorus antioxidants, thiol antioxidants, diphenylamine antioxidants, ascorbic acid antioxidants, and hindered amines It preferably contains at least one selected from the group consisting of antioxidants, more preferably contains at least one selected from the group consisting of phenolic antioxidants and phosphorus antioxidants, phenolic antioxidants It is further preferred to contain an agent. As for this antioxidant, it is preferable to use one or more of primary antioxidant and/or secondary antioxidant.
• the primary antioxidant captures peroxy radicals and prevents oxidative deterioration of the resin.
• known primary antioxidants can be used, but phenolic antioxidants are preferred, and hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide] , 4,4′-thiobis(6-tert-butyl-m-cresol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3 -tert-butylphenyl)butyric acid]glycol ester, 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert- butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6
• Phenolic antioxidants are 4,4'-thiobis (6-tert-butyl-m-cresol), thiodiethylene bis (6-tert-butyl-m-cresol), from the viewpoint of further suppressing cracking and peeling of the heat dissipating gap filler and maintaining appropriate hardness. It preferably contains at least one selected from the group consisting of [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 4,6-bis(octylthiomethyl)-o-cresol. .
• the secondary antioxidant decomposes the hydroxide radicals generated by the oxidation of double bonds to prevent oxidative deterioration of the resin.
• conventionally known secondary antioxidants can be applied, but phosphorus-based antioxidants are preferable, and trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl ) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecylphosphite, octyldiphenylphosphite, Di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaeryth
• the content of these antioxidants expresses the antioxidant effect without sacrificing other performance, when the total amount of the resin composition for heat-dissipating gap fillers of the present embodiment is 100% by mass, , for example, 0.01 to 20% by mass, preferably 0.4 to 20% by mass.
• the content of the antioxidant is 0.01% by mass or more when the total amount of the heat-dissipating gap filler resin composition of the present embodiment is 100% by mass, and is preferable from the viewpoint of further improving the antioxidant effect. is 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.4% by mass or more, and still more preferably 0.5% by mass or more, and thermal conductivity, handleability, etc.
• it is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, even more preferably 10.0% by mass or less, even more preferably 8.0% by mass or less, and even more preferably It is 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 1.0% by mass or less.
• the antioxidant may be contained in either A liquid or B liquid, or may be contained in both A liquid and B liquid.
• the content of the antioxidant contained in liquid A is preferably 0.025% by mass or more, more preferably 0.05% by mass, from the viewpoint of further improving the antioxidant effect when the total amount of liquid A is 100% by mass.
• % by mass or more more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and from the viewpoint of further improving the balance of thermal conductivity, handling properties, etc., preferably 25.0% by mass % or less, more preferably 20.0 mass % or less, more preferably 15.0 mass % or less, still more preferably 10.0 mass % or less, still more preferably 8.0 mass % or less, still more preferably 5.0 mass % % or less, more preferably 3.0 mass % or less, more preferably 1.5 mass % or less, still more preferably 1.0 mass % or less, still more preferably 0.5 mass % or less.
• the content of the antioxidant contained in liquid B is preferably 0.025% by mass or more, more preferably 0.05% by mass, from the viewpoint of further improving the antioxidant effect when the total amount of liquid B is 100% by mass. % by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and from the viewpoint of further improving the balance of thermal conductivity, handling properties, etc., preferably 25.0% by mass % or less, more preferably 20.0 mass % or less, more preferably 15.0 mass % or less, still more preferably 10.0 mass % or less, still more preferably 8.0 mass % or less, still more preferably 5.0 mass % % or less, more preferably 3.0 mass % or less, more preferably 1.5 mass % or less, still more preferably 1.0 mass % or less, still more preferably 0.5 mass % or less.
• the resin composition for heat-dissipating gap fillers of the present embodiment preferably further contains a curing accelerator.
• the curing accelerator is not particularly limited as long as it has the effect of accelerating the curing reaction, but an amine-based curing accelerator is preferred.
• the pKa of the amine curing accelerator is preferably 8.0 or higher, more preferably 9.0 or higher, and still more preferably 9.5 or higher.
• imidazoles such as 2-ethyl-4-ethylimidazole, 1-cyanoethyl-2-ethyl-4-ethylimidazole, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1 ,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo(4,3,0)nonene-5 (DBN), hexahydro-1,3,5-tris(3-dimethyl aminopropyl)-1,3,5-triazine, N,N,N',N'',N'-pentamethyldiethylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl Tertiary amines such as dicyclohexylamine, secondary amines such as 4,4'-methylenebis(N-sec-butylcyclohexanamine), N,N,N,
• the resin composition for a heat-dissipating gap filler of the present embodiment preferably further contains a plasticizer.
• the plasticizer is preferably a liquid at room temperature with a flash point of 200° C. or higher so as to stay inside the cured product.
• di-2-ethylhexyl phthalate DOP
• diisononyl phthalate DINP
• diisodecyl phthalate DIDP
• di-2-ethylhexyl adipate DOA
• diisononyl adipate DINA
• tri-trimellitate examples include esters such as 2-ethylhexyl (TOTM) and tricresyl phosphate (TCP), and fatty acid esters modified with animal and vegetable oils.
• the content of the plasticizer of the present embodiment is preferably 1 mass from the viewpoint of setting the viscosity of the resin in a more appropriate range when the total amount of the resin composition for a heat-dissipating gap filler of the present embodiment is 100% by mass. % or more, more preferably 2 mass % or more, still more preferably 3 mass % or more, and from the viewpoint of further improving the balance of thermal conductivity, handling properties, etc., preferably 10 mass % or less, more preferably 9 % by mass or less, more preferably 8% by mass or less.
• the resin composition for heat-dissipating gap fillers of the present embodiment preferably further contains a dispersant.
• the dispersant is not particularly limited as long as it has the effect of improving the wettability with the resin and improving the dispersibility for the purpose of modifying the surface of the thermally conductive filler.
• Anionic, nonionic and amphoteric surfactants can be mentioned, and one or more of them can be used.
• KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), EFKA (manufactured by BASF), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.) )), Disperbyk and BYK (manufactured by BYK-Chemie Co., Ltd.), Marialim (manufactured by NOF Corporation), Disparon (manufactured by Kusumoto Kasei Co., Ltd.), and the like. These may be blended during the production of liquid A or liquid B, or may be processed into fillers in advance.
• the content of the dispersant of the present embodiment is preferably 0 from the viewpoint of further improving the dispersibility of the thermally conductive filler when the total amount of the resin composition for a heat-dissipating gap filler of the present embodiment is 100% by mass. 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more, and from the viewpoint of further improving the balance of thermal conductivity, handleability, etc., preferably It is 1.0% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.6% by mass or less.
• the resin composition for a heat-dissipating gap filler of the present embodiment is obtained by mixing each material using a high-viscosity kneader such as a ball mill, three-roll mill, kneader, planetary mixer, and screw extruder. be done.
• a high-viscosity kneader such as a ball mill, three-roll mill, kneader, planetary mixer, and screw extruder.
• the resin composition for the heat-dissipating gap filler As a method of using the resin composition for the heat-dissipating gap filler, for example, the resin composition for the heat-dissipating gap filler is injected into the gap between the articles, or the resin composition for the heat-dissipating gap filler is applied and then the coated surface of the article is used. The articles are adhered to each other by sticking them together.
• the heat-dissipating gap filler is a two-liquid type, for example, liquid A and liquid B are mixed at a volume ratio of 1:1, and then injected into the gap between the articles, or applied and then the articles are pressed together on the coated surface. By sticking together, the articles are adhered to each other.
• the method of mixing by measuring the volume is generally used because it is simple.
• the heat-dissipating gap filler of the present embodiment is obtained by curing the resin composition for heat-dissipating gap fillers of the present embodiment. In the heat-dissipating gap filler of this embodiment, at least a part of the resin composition for heat-dissipating gap fillers of this embodiment may be cured.
• the heat-dissipating gap filler of the present embodiment is obtained, for example, by curing the resin composition for heat-dissipating gap filler of the present embodiment at room temperature (for example, 21° C. or higher and 25° C. or lower).
• room temperature for example, 21° C. or higher and 25° C. or lower.
• the initial curing time after mixing liquid A and liquid B varies depending on the type of curing accelerator, amount used, and temperature. It can be controlled in 5 to 60 minutes at room temperature (for example, 21° C. to 25° C.), which is said to be preferable, and then requires about 1 to 3 days for complete curing.
• room temperature for example, 21° C. to 25° C.
• it has excellent adhesiveness and moderate flexibility, so it will not peel off or crack for a long period of time even under severe conditions.
• Articles of the present embodiments comprise the exoergic gap filler of the present embodiments.
• Articles of the present embodiment are electronic devices such as digital home appliances, lithium-ion secondary batteries, and in-vehicle power modules.
• part represents a “mass part” in an example.
• Production example 1 (Production of A-1 solution) RICON 130MA8 (maleic anhydride-modified polybutadiene manufactured by Clay Valley) 2.70 parts, diisononyl phthalate (plasticizer manufactured by Shin Nippon Rika Co., Ltd.) 6.00 parts, B-325 (aluminum hydroxide manufactured by Armorix) 25 part, T-60 75MY (manufactured by Almatis Co., Ltd. aluminum oxide) 31 parts, LS-210B (manufactured by Nippon Light Metal Co., Ltd. aluminum oxide) 25 parts and ASFP-20 (manufactured by Denka Co., Ltd. aluminum oxide) 10.3 parts The mixture was mixed and stirred with a THINKY Co., Ltd. rotation/revolution type mixer ARE-310 to obtain 100 parts of A-1 liquid.
• THINKY Co., Ltd. rotation/revolution type mixer ARE-310 to obtain 100 parts of A-1 liquid.
• Production example 2 (Production of liquid B-1) Poly bd R-20LM (hydroxyl-modified polybutadiene manufactured by Clay Valley) 1.05 parts, Lupragen N700 (curing accelerator manufactured by BASF) 0.02 parts, diisononyl phthalate (plasticizer manufactured by Shin Nippon Rika Co., Ltd.)6. 63 parts, B-325 (Almorix aluminum hydroxide) 25 parts, T-60 75MY (Almatis aluminum oxide) 31 parts, LS-210B (Nippon Light Metal Co., Ltd.
• the obtained 8 types of A liquid and 33 types of B liquid were examined for changes in viscosity and properties after storage at 60 ° C. for 1 month. I didn't.
• Example 1 Mixing Liquid A-1 and Liquid B-3 and Making a Sheet Liquid A-1 and liquid B-3 were added to each of 100 ml tanks provided on both sides of a 200 ml Nordson 2-liquid parallel cartridge. The liquids were filled and passed through a 24-stage disposable spiral mixer (static mixer) to mix the A-1 liquid and the B-3 liquid at a volume ratio of 1:1. The obtained mixed solution is applied to a glass plate and crushed with an aluminum plate having a spacer of 1 mm thickness on both ends to prepare a sheet in which the AB mixed solution with a thickness of 1 mm is sandwiched between the glass plate and the aluminum plate. bottom.
• a 24-stage disposable spiral mixer static mixer
• liquids A and B were mixed according to the formulations shown in Tables 5 and 6 to obtain AB mixed liquids and sheets of Examples 1-24 and Comparative Examples 1-4.
• Thermal conductivity It was measured according to ASTM D5470 using a TIM tester from LINSEIS. In Examples 1 to 24 and Comparative Examples 1 to 4, samples for thermal conductivity measurement were samples obtained by curing the above sheets. The sheet was cured under the conditions of curing temperature: 25° C. and curing time: the complete curing time shown in Tables 5 and 6.
• Thermal shock test The sheets obtained in Examples and Comparative Examples were held at ⁇ 40° C. for 20 minutes, heated to 100° C. in 10 minutes, held for 20 minutes, and cooled to ⁇ 40° C. in 10 minutes for a total of 60 minutes. After 2000 cycles, the degree of cracking/peeling was evaluated according to the following indices. A (very good): neither cracking nor peeling B (good): only one of cracking or peeling is observed C (poor): both cracking and peeling are observed
• the hardness of the 3 mm-thick AB mixed liquid sandwiched sheet was measured in the same manner as in the above "hardness”. At the time of hardness measurement, the point where the indenter of the hardness tester (indenter shape: hemispherical, tip R: 1.19 mm) was stuck was observed with an optical microscope at a magnification of 40 times. Fragility 2 is a criterion for evaluating fragility on a stricter basis than fragility 1. Brittleness 2 was evaluated according to the following index.
• brittleness 1 and brittleness 2 both rated A
• the evaluation of cracking/peeling after the thermal shock test in the examples and the evaluation of cracking/peeling and brittleness after the aging test were all better than those of the comparative examples. That is, according to the resin composition for a heat-dissipating gap filler of the present embodiment, even if the heat-dissipating gap filler is exposed to high-temperature conditions for a long time or undergoes a sudden temperature change, cracking or peeling occurs. can be reduced. In addition, it is possible to maintain an appropriate hardness under conditions corresponding to actual usage scenes.
• the two-liquid type heat-dissipating gap filler resin composition has good storage stability before mixing liquid A and liquid B, and has an initial curing time of 5 to 60 minutes at room temperature after mixing. It was found that the operability was good due to its curability. Since the resin composition for heat-dissipating gap fillers of the present embodiment does not need to contain volatile silicones or low-molecular-weight siloxanes that cause contact failure, voids due to water or gas present in the system or generated during the curing reaction can be eliminated. no occurrence.

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