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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/407—Aluminium oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/12—Treatment with organosilicon compounds
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to thermally conductive compositions.
• thermo design As the word “thermal design” suggests, it is becoming important to remove heat from a heating element. Recently, countermeasures against heat have been actively researched and implemented in fields such as automobile ECUs (Electronic Control Units), batteries, and base stations (5G base stations) based on the 5th generation mobile communication system (5G). Heat-generating elements mounted on these components may malfunction or become a factor of failure as the temperature rises. Therefore, various heat dissipating materials are used as heat countermeasures. As the heat-dissipating material, grease, a heat-dissipating sheet, an adhesive, or the like, in which a thermally conductive filler is added to an elastomer, is used.
• the heat generated by the heat generating element tends to increase more and more, and a material with high thermal conductivity is required to quickly transfer the heat out of the system.
• a material with high thermal conductivity is required to quickly transfer the heat out of the system.
• it is easy to increase the filling amount of the filler it is easy to increase the filling amount of the filler, and the effect is enormous.
• surface treatment of the filler is performed as a method for facilitating the filling of the filler.
• a frequently used surface treatment agent is a silane coupling agent.
• the silane coupling agent has both an alkoxy group that binds to the surface of the filler and a hydrophobic group that binds to the polymer material in its molecule, and functions to connect the filler and the polymer material.
• the hydrophobic groups are mostly composed of hydrocarbons, which makes them more compatible with elastomers. Therefore, the filler surface-treated with the silane coupling agent can increase the filling amount of the elastomer.
• heat dissipation materials made of soft materials have been used so as not to apply a load to substrates and heating elements as much as possible, and silane coupling agents, which do not have bonding points with polymers, are mainly used as surface treatment agents for fillers. It is used.
• silane coupling agents are sometimes called silane agents. Since the filler surface-treated with a silane agent can further increase the filling amount of the elastomer and can reduce the hardness of the resulting cured product, the silane agent can be said to be a good surface treatment agent at present.
• the hydrophobic group of the silane coupling agent By increasing the number of carbon atoms in the hydrophobic group of the silane coupling agent, it becomes more compatible with the elastomer. Hydrophobic groups up to about 18 carbon atoms can be obtained, but when the number of carbon atoms increases, the alkoxy group becomes difficult to hydrolyze, making it difficult to prepare a solution to be dispersed in the filler, Molecularization and formation of a polymer film may be slow or may not occur, and there is a problem that a large amount of unreacted silane coupling agent remains in the polymer system. In addition, the unreacted silane coupling agent volatilizes, causing problems such as contamination of the device and deterioration of the heat resistance of the heat dissipating material.
• Patent Document 1 proposes a method of surface-treating a thermally conductive inorganic powder with a silane compound having 6 or more carbon atoms or a partial hydrolyzate thereof by a dry method or a wet method.
• Patent Document 2 a first silicone material having a plurality of SiH groups on the surface of a particle material mainly composed of an inorganic oxide formed by oxidation of a predetermined element and having an OH group on the surface is described above.
• Patent Literature 3 proposes a method of surface-treating a thermally conductive filler by an integral method using dimethylpolysiloxane having one molecular chain end blocked with a trialkoxysilyl group.
• a thermally conductive composition containing a filler surface-treated with the silane compound has high thermal conductivity and can be cured. It can reduce the hardness of the object.
• pretreatment is carried out by a dry method or a wet method as a surface treatment method of the filler, the amount of remaining silane compound is small.
• the polymerization of the silane compound and the formation of a polymer film do not proceed, and the heat resistance of the cured product is lowered.
• alkoxy groups remain in the system because the silane compound has not been polymerized or formed into a polymer film. Therefore, in the condensation reaction system, there is a problem that the reaction is abnormally fast, such as the composition being cured during mixing, and a problem that the hardness of the cured product is abnormally high.
• the second silicone material may remain in the system. If there are many SiH groups remaining on the surface of the filler, the composition containing the filler is imparted with thixotropic properties and the fluidity is reduced, making it difficult to apply or print the composition, or when forming the composition into a sheet. There was a problem such as a decrease in workability. Moreover, the remaining second silicone material has the problem of adversely affecting the hardness control, storage stability, and reaction speed of the composition.
• dimethylpolysiloxane in which one end of the molecular chain is blocked with a trialkoxysilyl group is used as the surface treatment agent, so the filler surface-treated with the dimethylpolysiloxane has compatibility with silicone.
• the dimethylpolysiloxane since the dimethylpolysiloxane has a trialkoxy group, the dimethylpolysiloxane behaves as a cross-linking agent in the condensed silicone system, and there is a problem that it is impossible to adjust the hardness of the thermally conductive composition and control the reaction time. .
• the present invention has been made in view of such circumstances, and provides a cured product having a moderate reaction rate, high thermal conductivity, excellent heat resistance, moderate hardness and excellent restorability. It is an object to provide a thermally conductive composition that can be obtained.
• a thermally conductive composition comprising a filler and a polymer component, wherein the filler comprises at least one surface-treated filler selected from the group consisting of the following filler (A) and filler (B).
• R 1 and R 2 are each independently an alkylene group having 2 to 6 carbon atoms, and R 3 is an alkyl group having 1 to 3 carbon atoms. R 2 of may be the same or different, n is an integer of 1 to 9, * indicates a bonding portion with a silicon atom.
• [2] The thermally conductive composition according to [1] above, wherein the total content of the filler (A) and the filler (B) contained in the filler is 30% by mass or more and 100% by mass or less.
• thermosetting resins elastomers
• oils elastomers
• the content of the filler is 30.0% by mass or more and 99.8% by mass or less
• the content of the polymer component is 0.2% by mass or more and 70% by mass.
• the thermally conductive composition according to any one of [1] to [4] above which is .0% by mass or less.
• Hardness increase rate (%) (S A ⁇ S 0 )/S 0 ⁇ 100 (ii) (In the formula, S0 is the initial hardness of the test piece made of the cured product of the thermally conductive composition, and S A is the hardness of the test piece after exposure at a temperature of 130°C or 200°C for 168 hours.)
• S0 is the initial hardness of the test piece made of the cured product of the thermally conductive composition
• S A is the hardness of the test piece after exposure at a temperature of 130°C or 200°C for 168 hours.
• thermoly conductive composition that has a moderate reaction rate, high thermal conductivity, excellent heat resistance, moderate hardness, and excellent restorability. can do.
• the "number of hydroxyl groups” means the average number of hydroxyl groups contained in one molecule of the castor oil-based polyol.
• “castor oil-based” means natural oils and fats containing a triester compound of ricinoleic acid and glycerin, processed natural oils and fats, or synthetic oils and fats containing a synthetically obtained triester compound.
• a "castor oil-based polyol” means an ester compound of ricinoleic acid and/or hydrogenated ricinoleic acid and a polyhydric alcohol. The ester compound may be a compound modified using castor oil obtained by squeezing the seeds of castor (Ricinus communis L.) or a derivative thereof as a starting material. It may be the resulting polyol.
• the thermally conductive composition of the present embodiment contains a filler and a polymer component, and the filler contains at least one surface-treated filler selected from the group consisting of the following filler (A) and filler (B). include.
• R 1 and R 2 are each independently an alkylene group having 2 to 6 carbon atoms, and R 3 is an alkyl group having 1 to 3 carbon atoms.
• R 2 of may be the same or different, n is an integer of 1 to 9, * indicates a bonding portion with a silicon atom.
• the thermally conductive composition of the present embodiment contains at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) as a filler, thereby achieving an appropriate reaction rate. It is possible to obtain a cured product having high thermal conductivity, excellent heat resistance, appropriate hardness, and excellent restorability.
• the filler used in the present embodiment contains at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B).
• the filler may contain fillers other than the filler (A) and the filler (B) as long as the effects of the present invention are not impaired.
• Other fillers may or may not be surface-treated.
• the term "filler" refers to a material that has not been surface-treated.
• the thermal conductivity of the filler is preferably 0.5 W/m ⁇ K or more, more preferably 1 W/m ⁇ K or more.
• Examples of the filler include metals; silicon; oxides, nitrides, carbides, hydroxides, fluorides, and carbonates of metals, silicon, or boron; and carbon.
• Examples of the metal include silver, gold, copper, iron, tungsten, stainless steel, aluminum, and carbonyl iron, and those that can be easily handled in the air are preferably used.
• Examples of the oxide include zinc oxide, aluminum oxide, magnesium oxide, silicon oxide, titanium oxide, iron oxide, calcium oxide, and cerium oxide.
• Composite oxides are also used.
• silicon oxide includes natural products and synthetic products, and specific examples include smokeless silica, wet silica, dry silica, fused silica, quartz powder, silica sand, silica stone, and silicic anhydride.
• Examples of composite oxides include spinel, perovskite, barium titanate, laurel, and ferrite.
• the nitride include aluminum nitride, boron nitride, and silicon nitride.
• Examples of the carbide include silicon carbide and boron carbide.
• Examples of the hydroxide include aluminum hydroxide, magnesium hydroxide, iron hydroxide, cerium hydroxide, and copper hydroxide.
• Examples of the fluorides include magnesium fluoride and calcium fluoride.
• Examples of the carbonate include magnesium carbonate and calcium carbonate, and carbonate complex salts such as dolomite are also used. Examples of the carbon include graphite and carbon black. These may be used singly or in combination of two or more.
• the filler is preferably at least one selected from the group consisting of metals, silicon, metal oxides, nitrides, and composite oxides from the viewpoints of various particle sizes, various shapes, prices, and availability. , metal oxides are more preferred.
• aluminum oxide alumina
• ⁇ -alumina is particularly preferable because of its high thermal conductivity.
• aluminum nitride and boron nitride are preferably used, and from the viewpoint of low cost, silica, quartz powder, and aluminum hydroxide are preferably used.
• the shape of the filler is not particularly limited as long as it is a particle, and examples include a spherical shape, a spherical shape, a rounded shape, a scaly shape, a crushed shape, and a fiber shape. These may be used in combination.
• the filler preferably has a specific surface area of 0.05 m 2 /g or more and 10.0 m 2 /g or less, more preferably 0.06 m 2 /g or more and 9.0 m 2 /g or less, as determined by the BET method. and more preferably 0.08 m 2 /g or more and 8.0 m 2 /g or less.
• the specific surface area is 0.05 m 2 /g or more, the filler can be highly filled and the thermal conductivity can be improved.
• the specific surface area of the filler can be measured by a BET one-point method based on nitrogen adsorption using a specific surface area measuring device, and specifically, it can be measured by the method described in the Examples.
• the average particle diameter of the filler is preferably 0.001 ⁇ m or more and 200 ⁇ m or less, more preferably 0.005 ⁇ m or more and 180 ⁇ m or less, still more preferably 0.01 ⁇ m or more and 150 ⁇ m or less, and even more preferably 0.05 ⁇ m. It is more than 100 micrometers or less.
• the average particle size of the filler is 0.001 ⁇ m or more, it is easy to fill the polymer, and an improvement in thermal conductivity can be expected accordingly. be able to.
• fillers having different particle sizes may be used in combination as long as the average particle size is within the above range.
• the "average particle size" means the volume average particle size, and the particle size at which the cumulative volume is 50% (50 % particle diameter D50).
• the filler may be previously subjected to other surface treatments such as water resistance treatment and fluidity improvement.
• Surface treatments such as water resistance treatment and fluidity improvement may be applied to the entire surface of the filler, or may be applied to a portion thereof.
• the surface-treated filler include a filler obtained by uniformly applying nanoparticles such as graphene to aluminum nitride, a filler obtained by uniformly applying silica to a ceramics filler, a sol-gel method or water glass on the surface of aluminum nitride, etc.
• a silicon oxide film is prepared with water-resistant and insulating film-forming fillers.
• the filler surface of the filler (A) is treated by chemical vapor deposition using siloxane having one SiH group.
• the filler surface has functional groups such as hydroxyl groups, and by chemical vapor deposition, the functional groups and the SiH groups of siloxane are easily chemically bonded, the siloxane is fixed on the filler surface, and the siloxane is attached to the filler surface. A group based on is introduced.
• the filler to be surface-treated by the chemical vapor deposition method those described in the section [Filler] can be used.
• the surface treatment is preferably applied to a part of the surface of the filler.
• the rate of introduction of the siloxane-based group to the filler surface is preferably 0.01 to 1.0% by mass, more preferably 0.01, from the viewpoint of the viscosity and consistency of the composition before curing. 0.8% by mass, more preferably 0.01 to 0.6% by mass.
• the rate of introduction of the siloxane-based group can be measured by a method conforming to JIS R1675:2007 "combustion (high-frequency heating)-infrared absorption method". Specifically, it can be measured by the method described in Examples.
• Examples of the siloxane having one SiH group used for surface treatment of the filler include benzyldimethylsilane, tert-butyldimethylsilane, 1,1,1,3,3-pentamethyldisiloxane, 1,1,1, 3,5,5,5-heptamethyltrisiloxane (MDHM) and the like. Among them, MDHM is preferable from the viewpoint of boiling point and availability. These may be used singly or in combination of two or more.
• a chemical vapor deposition (CVD) method is a method of depositing a film by chemical reaction of a raw material gas containing a target thin film component on a substrate surface or in a vapor phase. Depending on the target component, surface treatment may be performed by chemical vapor deposition while pressurizing, decompressing, or generating plasma.
• the siloxane having one SiH group is gas, it is directly vaporized, and when it is liquid, it is vaporized to form the siloxane film on the surface of the filler.
• a container containing siloxane having one SiH group and a container containing a filler are placed together in a heating device such as an oven and heated to a predetermined temperature.
• the siloxane having one SiH group is vaporized and diffused, adsorbed, and chemically reacted with the filler, so that the surface of the filler can be treated.
• the surface treatment of the filler can be performed by heating the siloxane having one SiH group, introducing an inert gas as a carrier gas to the filler, and causing diffusion, adsorption, and chemical reaction.
• Fillers that are surface-treated by chemical vapor deposition are preferably stored in a constant temperature and humidity tank in order to keep the number of functional groups such as hydroxyl groups constant on the surface.
• Storage conditions are preferably in the temperature range of 15° C. or higher and 35° C. or lower and the humidity range of 30% RH or higher and 80% RH or lower.
• the heating temperature in the chemical vapor deposition method varies depending on the siloxane used, but is preferably 40°C or higher and 120°C or lower, more preferably 40°C or higher and 100°C or lower. Also, it is preferable to heat the piping for introducing the gas.
• the heating time is preferably 2 hours or more and 10 hours or less, more preferably 4 hours or more and 8 hours or less.
• siloxane that does not participate in the reaction does not remain in the filler. has disappeared. Heating under reduced pressure may be applied to remove excess siloxane remaining. Moreover, the siloxane that did not participate in the reaction can be recovered and reused.
• an apparatus capable of stirring such as a kneader, a planetary mixer, a Henschel mixer, a Nauta, a high-speed mixer, and a fluidized bed dryer can be used. These are preferably those that can be heated, and since hydrogen is generated by the reaction, they are preferably explosion-proof.
• the surface treatment by the chemical vapor deposition method can also be performed by placing the filler in a stainless vat, allowing it to stand in a heated oven, and flowing siloxane gas.
• fillers of different particle sizes and different chemical types can be treated at the same time, and furthermore, it is possible to prevent coloring due to abrasion of the container and stirring blades, which is a concern in rotating system stirring. preferable.
• the filler (B) is a filler surface-treated by chemical vapor deposition using a siloxane having two or more SiH groups, and further includes an unsubstituted alkyl group having 6 to 20 carbon atoms, a substituted At least one group selected from the group consisting of an alkyl group having 2 to 20 carbon atoms having a group and a group represented by the following general formula (I) is introduced in combination.
• R 1 and R 2 are each independently an alkylene group having 2 to 6 carbon atoms, and R 3 is an alkyl group having 1 to 3 carbon atoms.
• R 2 of may be the same or different, n is an integer of 1 to 9, * indicates a bonding portion with a silicon atom.
• the fillers that are surface-treated by the chemical vapor deposition method can be those described in the above [Fillers] section. Moreover, the surface treatment by the chemical vapor deposition method is as described in the above [Filler (A)] section.
• the siloxane used for the surface treatment of the filler is not particularly limited as long as it has two or more SiH groups, but from the viewpoint of the boiling point of the raw material described later, the number of functional groups to be introduced, and availability, the number of SiH groups is 2 to 8. It is preferable to have 2 or more, and it is more preferable to have 2 or more and 4 or less.
• the siloxane has SiH groups within the above range, the composition is imparted with appropriate thixotropic properties.
• siloxane having two or more SiH groups examples include 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), 1,3,5,7,9-pentamethylcyclopentasiloxane (D5H), 1,1,3,3-tetramethyldisiloxane (TMDO), 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,3,5,7,7,7-octa methyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodeca Methylhexasiloxane, 1,3,3,5,5,7,7,9,9,11,11,13-tetradecamethylheptasiloxane, 1,1,5,5-tetramethyl-3,3 - diphenyltrisiloxane and the like.
• D4H and TMDO 1,1,3,
• siloxane having two or more SiH groups is used for the surface treatment of the filler by chemical vapor deposition
• unreacted SiH groups are present on the surface of the filler.
• At least one group selected from the above is introduced.
• the group to be introduced into the surface of the filler is preferably a group represented by the general formula (I).
• the unsubstituted alkyl group having 6 to 20 carbon atoms may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, preferably a straight-chain alkyl group.
• the number of carbon atoms in the alkyl group is preferably 6-18, more preferably 6-12.
• Examples of the alkyl group include hexyl group, heptyl group, octyl group, decyl group, dodecyl group and the like. Among them, a decyl group is preferable from the viewpoint of the boiling point of the starting material and compatibility with the polymer, which will be described later. These may be one kind or two or more kinds.
• the substituted alkyl group having 2 to 20 carbon atoms may be a linear alkyl group or a branched alkyl group, and is preferably a linear alkyl group.
• the number of carbon atoms in the alkyl group is preferably 2-18, more preferably 2-12.
• alkyl group examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, A hexadecyl group, an octadecyl group and the like can be mentioned.
• a hexyl group, an octyl group, and a decyl group are preferred, and a decyl group is more preferred, from the viewpoint of the boiling point of the starting material and compatibility with the polymer, which will be described later.
• These may be one kind or two or more kinds.
• a polyether group etc. are mentioned as a substituent which the said alkyl group has.
• the polyether group include a polyethyleneoxy group [(C 2 H 4 O) x , where x is an integer of 1 to 4] and a polypropyleneoxy group [(C 3 H 6 O) y , where y is an integer of 1 to 4].
• R 1 and R 2 are each independently an alkylene group having 2 to 6 carbon atoms, and R 3 is an alkyl group having 1 to 3 carbon atoms. When multiple R 2 are present, the multiple R 2 may be the same or different.
• n is an integer of 1-9. * indicates a bonding portion with a silicon atom.
• the alkylene group having 2 to 6 carbon atoms of R 1 and R 2 is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms. Examples of the alkylene group include ethylene group, n-propylene group, n-butylene group, n-hexylene group and the like.
• an ethylene group is preferable from the viewpoint of the boiling point and availability of raw materials, which will be described later.
• the alkyl group having 1 to 3 carbon atoms for R 3 include methyl group, ethyl group, n-propyl group and isopropyl group.
• a methyl group or an ethyl group is preferable from the viewpoint of the boiling point and availability of raw materials to be described later.
• n is an integer of 1-9, preferably an integer of 1-4, more preferably an integer of 1-3.
• the group to be introduced into the filler may be a combination of the group represented by the general formula (I) and an unsubstituted alkyl group having 6 to 20 carbon atoms. may be a combination of alkyl groups having 2 to 20 carbon atoms and substituents.
• a filler into which a group having a large number of carbon atoms is introduced is easily filled into a polymer component, and a composition containing it has high thixotropic properties, it can be suitably used for adhesives and the like.
• the filler contains at least one selected from the group consisting of unsubstituted alkyl groups having 6 to 20 carbon atoms, substituted alkyl groups having 2 to 20 carbon atoms, and groups represented by the general formula (I).
• the method of introducing the group is not particularly limited, for example, the unsubstituted alkyl group having 6 to 20 carbon atoms is a SiH group present on the surface of the filler and an unsubstituted ⁇ -olefin having 6 to 20 carbon atoms.
• the substituted alkyl group having 2 to 20 carbon atoms can be introduced by a hydrosilylation reaction between the SiH group present on the surface of the filler and an ⁇ -olefin having 2 to 20 carbon atoms having a substituent.
• the group represented by the general formula (I) can be introduced by a hydrosilylation reaction between a SiH group present on the surface of the filler and a monofunctional (meth)acrylate having an oxyalkylene group.
• the unsubstituted ⁇ -olefin having 6 to 20 carbon atoms may be a linear olefin or a branched olefin, and is preferably a linear olefin.
• the unsubstituted ⁇ -olefin having 6 to 20 carbon atoms is preferably an ⁇ -olefin having 6 to 18 carbon atoms, more preferably an ⁇ -olefin having 6 to 12 carbon atoms.
• Examples of the unsubstituted ⁇ -olefins having 6 to 20 carbon atoms include 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, vinylcyclohexane and allylcyclohexane.
• 1-decene is preferable from the viewpoint of boiling point and compatibility with the polymer. These may be used singly or in combination of two or more.
• the substituted ⁇ -olefin having 2 to 20 carbon atoms may be a linear olefin or a branched olefin, and is preferably a linear olefin.
• the substituted ⁇ -olefin having 2 to 20 carbon atoms is preferably an ⁇ -olefin having 2 to 18 carbon atoms, more preferably an ⁇ -olefin having 2 to 12 carbon atoms.
• Examples of the ⁇ -olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -hexadecene, 1-octadecene, vinylcyclohexane, allylcyclohexane and the like.
• 1-decene is preferable from the viewpoint of boiling point and compatibility with the polymer. These may be used singly or in combination of two or more.
• a polyether group etc. are mentioned as said substituent.
• polyether group examples include a polyethyleneoxy group [(C 2 H 4 O) x , where x is an integer of 1 to 4] and a polypropyleneoxy group [(C 3 H 6 O) y , where y is an integer of 1 to 4]. , a polyalkyleneoxy group in which an ethyleneoxy group (EO) and a propyleneoxy group (PO) are added blockwise or randomly, and the like.
• EO ethyleneoxy group
• PO propyleneoxy group
• Examples of the monofunctional (meth)acrylate having an oxyalkylene group include methoxy-triethylene glycol acrylate, ethoxy-diethylene glycol acrylate and methoxy-tripropylene glycol acrylate. Among them, ethoxy-diethylene glycol acrylate is preferable from the viewpoint of boiling point and compatibility with the polymer. These may be used singly or in combination of two or more.
• the hydrosilylation reaction SiH groups and vinyl groups are reacted in the presence of a platinum catalyst.
• the hydrosilylation reaction is preferably carried out at a temperature of 25° C. to 150° C. for 5 minutes to 24 hours, more preferably at a temperature of 70° C. to 130° C. for 30 minutes to 2 hours. .
• the introduction rate of at least one group is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.8% by mass, from the viewpoint of the viscosity and consistency of the composition before curing. Yes, more preferably 0.02 to 0.6% by mass.
• the introduction rate can be measured by a method conforming to JIS R1675:2007 "combustion (high-frequency heating) - infrared absorption method". Specifically, it can be measured by the method described in Examples.
• the thermally conductive composition of the present embodiment contains at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) as a filler, thereby providing an appropriate reaction.
• a cured product having high speed, high thermal conductivity, excellent heat resistance, appropriate hardness and excellent restorability can be obtained.
• silane coupling agents having trialkoxy groups and silane agents used as surface treatment agents have residual trialkoxy groups when the trialkoxy groups do not participate in polymerization or polymer film formation.
• the filler titanium oxide
• the trialkoxy group-containing filler causes the thermal history of the thermally conductive composition to polymerize the thermally conductive composition and polymerize the reaction.
• it affects physical properties such as hardness, compression set, tensile strength, elongation, tear strength, and heat resistance of the cured product.
• the remaining trialkoxy group dissolves the surface of metal such as aluminum, and the hardening reaction progresses too much after long-term use, which may cause problems such as aluminum sticking too strongly to each other and not being removed.
• at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) in the present embodiment the effect of the residual groups of the surface treatment agent can be greatly reduced, and the hardness of the cured product can be reduced. stiffness, compression set, and heat resistance can be improved. Furthermore, physical properties such as tensile strength, elongation and tear strength can also be improved.
• the total content of the filler (A) and the filler (B) contained in the filler is preferably 30% by mass or more and 100% by mass or less, more preferably 35% by mass or more and 90% by mass or less, More preferably, it is 40% by mass or more and 80% by mass or less.
• the total content of the filler (A) and the filler (B) is within the above range, the hardness of the cured product can be lowered. Further, when the total content of the filler (A) and the filler (B) is 30% by mass or more, the viscosity of the composition can be lowered.
• the filler may include at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) and a non-surface-treated filler. From the viewpoint of high thermal conductivity, aluminum oxide is preferable as the non-surface-treated filler.
• the content thereof is preferably 10% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 80% by mass or less.
• the content of the non-surface-treated filler is within the above range, it is possible to impart moisture resistance and heat resistance.
• the filler may include a filler treated with a surface treatment agent (hereinafter also referred to as another surface treatment agent) other than the surface treatment agents used in the (A) filler and the (B) filler.
• a surface treatment agent hereinafter also referred to as another surface treatment agent
• examples of other surface treatment agents include silane coupling agents (silane agents), titanium coupling agents, aluminum coupling agents, fatty acids, fatty acid esters, higher alcohols, silicone oils, fluorine oils, dispersants, surfactants, and the like. is mentioned. Any other surface treatment agent may be used as long as it does not affect the cured form and physical properties and does not interfere with the effects of the present invention.
• the filler may also include a filler into which a single-ended vinylpolysiloxane (single-ended vinylsilicone) is introduced.
• a filler into which a single-ended vinylpolysiloxane has been introduced has excellent compatibility with silicone, so it is preferably used when silicone is used as the polymer component described later.
• the filler contains a filler into which one-end vinylpolysiloxane is introduced, the content thereof is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 50% by mass or less, relative to the total amount of the filler. It is 40% by mass or less.
• the content of the filler is preferably 30.0% by mass or more and 99.8% by mass or less, more preferably 50.0% by mass or more and 99.5% by mass, relative to the total amount of the thermally conductive composition of the present embodiment. % by mass or less, more preferably 60.0% by mass or more and 99.0% by mass or less, and even more preferably 70.0% by mass or more and 95.0% by mass or less.
• the content of the filler is 30.0% by mass or more, high thermal conductivity can be imparted, and when it is 99.8% by mass or less, the fluidity of the composition can be secured, and the composition can be molded. can be made as hard as possible.
• the polymer component used in this embodiment is not particularly limited, and examples thereof include thermosetting resins, thermoplastic resins, elastomers, and oils. You may use these individually or in mixture of 2 or more types. From the viewpoint of obtaining the effects of the present invention, the polymer component is preferably at least one selected from the group consisting of thermosetting resins, elastomers, and oils. Note that the thermosetting resin means a product in a state before curing, and in this specification, it is not limited to the heat-curing type, but also includes the normal-temperature curing type.
• thermosetting resins include epoxy resins, phenol resins, unsaturated polyester resins, melamine resins, urea resins, polyimides, and polyurethanes.
• thermoplastic resins include polyolefins such as polyethylene and polypropylene; , thermoplastic polyimide, polylactic acid, polycarbonate, and the like.
• the thermosetting resin and thermoplastic resin may be modified with silicone or fluororesin. Specific examples of modified resins include silicone-modified acrylic resins and fluororesin-modified polyurethanes.
• elastomers include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene, styrene-butadiene, chloroprene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber (EPM, EPDM), chlorosulfonated polyethylene, and acrylic rubber. , epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluororubber, polyurethane rubber, and the like.
• oils include low-molecular-weight poly- ⁇ -olefins, low-molecular-weight polybutenes, silicone oils, and fluorine oils. You may use these individually or in mixture of 2 or more types.
• the polymer component is preferably polyurethane, silicone rubber, or silicone oil.
• the polymer component preferably has a viscosity at 25° C. of 30 mPa ⁇ s to 3000 mPa ⁇ s, more preferably 50 mPa ⁇ s to 2800 mPa ⁇ s.
• a viscosity at 25° C. is measured using a rotational viscometer (for example, Toki Sangyo Co., Ltd., product name: TVB-10, rotor No. 3) in accordance with JIS Z8803: 2011. Measurement can be performed at a speed of 20 rpm.
• the content of the polymer component is preferably 0.2% by mass or more and 70.0% by mass or less, more preferably 0.5% by mass or more and 50.0% by mass or more, relative to the total amount of the thermally conductive composition of the present embodiment. It is 0 mass % or less, more preferably 1.0 mass % or more and 40.0 mass % or less, and even more preferably 2.0 mass % or more and 30.0 mass % or less.
• thermal conductivity can be imparted, and when it is 70.0% by mass or less, the hardness of the cured product and the viscosity of the composition can be made appropriate. can.
• a resin that could not be used as a polymer component of the thermally conductive composition can be used.
• resins include condensed silicones and alkoxysilyl-containing polyurethanes.
• the condensed silicone is a system composed of a hydroxyl-terminated polysiloxane, a silane agent or a silane coupling agent as a cross-linking agent, and a metal complex. These three types are mixed and cured in the presence of water.
• the reaction rate is controlled by adding at least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) to the three components.
• the hardness of the resulting cured product can be controlled.
• metal complexes may be added as accelerators. Since the metal complex reacts with the trialkoxy group of the silane agent or silane coupling agent, there is a problem that the reaction rate and the hardness of the cured product cannot be controlled.
• At least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) instead of the silane coupling agent, the reaction The speed can be controlled and the hardness of the resulting cured product can be controlled.
• At least one surface-treated filler selected from the group consisting of the filler (A) and the filler (B) is preferably used when there is a contradiction in the curing system in the system.
• the filler (A) and the filler (B) have residual SiH removed in the surface treatment process, they can also be used for curing resins that use a hydrosilylation reaction.
• curable resins include vinyl group-containing silicones and acrylics. Since the surface of the filler is covered with the above-mentioned specific siloxane, the activity of the filler is lowered, which prevents deactivation of the platinum catalyst and reduces the deactivation of Si of the cross-linking agent. Furthermore, since the surface of the filler is covered with the above-mentioned specific siloxane, the interfacial energy of the resin other than silicone and fluororesin is lowered, and the fluidity of the composition is improved.
• the thermally conductive composition of the present embodiment has no effect on the cured form and physical properties, and does not impair the effects of the present invention.
• Additives such as agents, dispersants, and reaction accelerators can be blended as necessary.
• the amount added is preferably 0.05% by mass or more and 20.0% by mass or less, more preferably 0.10% by mass or more, relative to the total amount of the thermally conductive composition. It is 20.0% by mass or less, more preferably 0.14% by mass or more and 17.0% by mass or less.
• the total content of the filler and the polymer component is preferably 85-100% by mass, more preferably 90-100% by mass, and still more preferably 92-100% by mass. 100% by mass.
• the thermally conductive composition of the present embodiment can be obtained by putting the filler, the polymer component, and other additives into a stirring device and stirring and kneading them.
• the stirring device is not particularly limited, and examples thereof include a twin roll, a kneader, a planetary mixer, a high-speed mixer, and a rotation/revolution stirrer.
• the thermally conductive composition of the present embodiment preferably has a viscosity at 30° C. of 80 Pa ⁇ s or more and 1000 Pa ⁇ s or less, more preferably 100 Pa ⁇ s or more and 500 Pa ⁇ s or less, and still more preferably 120 Pa ⁇ s or more and 250 a. ⁇ It is less than or equal to s.
• the viscosity can be measured by a method conforming to JIS K7210:2014 using a flow viscometer, and specifically by the method described in Examples.
• the thermally conductive composition of the present embodiment preferably has a consistency at 23° C. of 30 to 450, more preferably 40 to 420, even more preferably 50 to 390, and even more preferably 100 385 or less, more preferably 150 or more and 380 or less, and even more preferably 200 or more and 380 or less.
• the consistency is an index indicating the flexibility of the thermally conductive composition, and the larger the value, the softer the thermally conductive composition.
• the consistency of the thermally conductive composition is within the above range, the thermally conductive composition is excellent in flexibility.
• the consistency can be measured by a method conforming to JIS K2220:2013, specifically by the method described in Examples.
• the thermally conductive composition of the present embodiment has a moderate reaction rate, high thermal conductivity, excellent heat resistance, moderate hardness, and excellent restorability. It can be suitably used for exothermic electronic parts such as electronic devices, personal computers, ECUs and batteries for automobiles.
• the thermally conductive composition of the present embodiment can be obtained by, for example, injecting it into a mold or the like, drying it if necessary, and then heat-curing it to obtain a cured product. Further, when the polymer component is a room temperature curing type, it may be cured by leaving it at a temperature of 20 to 25° C. for about 5 to 10 days. The drying may be performed at room temperature or natural drying. The heating is preferably performed at a temperature of 50° C. to 150° C. for 5 minutes to 20 hours, more preferably at a temperature of 60° C. to 100° C. for 10 minutes to 10 hours. .
• the cured product of the thermally conductive composition of the present embodiment preferably has a thermal conductivity of 1.0 W/m ⁇ K or more, more preferably 1.5 W/m ⁇ K or more, and still more preferably 2. It is 0 W/m ⁇ K or more.
• the thermal conductivity can be measured by a method conforming to ISO22007-2, and specifically by the method described in Examples.
• the cured product of the thermally conductive composition of the present embodiment preferably has a C hardness of 20 or more and 75 or less, more preferably 30 or more, as measured according to the hardness test (type C) of JIS K7312:1996. It is 70 or less, more preferably 40 or more and 70 or less, still more preferably 45 or more and 70 or less.
• the cured product can have an appropriate hardness.
• the C hardness can be specifically measured by the method described in Examples.
• the cured product of the thermally conductive composition of the present embodiment preferably has an A hardness of 20 or more and 85 or less, more preferably 30 or more, measured according to the hardness test (type A) of JIS K7312:1996. It is 85 or less, more preferably 40 or more and 85 or less. When the A hardness is within the above range, a cured product having an appropriate hardness can be obtained.
• the A hardness can be specifically measured by the method described in Examples.
• the cured product of the thermally conductive composition of the present embodiment has a Shore 00 hardness measured according to ASTM D2240 of preferably 20 or more and 85 or less, more preferably 30 or more and 85 or less, and still more preferably 40 or more and 85. It is below. When the Shore 00 hardness is within the above range, the cured product can have an appropriate hardness.
• the Shore 00 hardness can be specifically measured by the method described in Examples.
• the thickness (mm) of the test piece after compression, T C is the thickness (mm) of the spacer in the compression device)
• restorability shows that it is restoring to the original thickness, so that a numerical value is small.
• the resilience can be measured with reference to JIS K6301, and specifically by the method described in Examples.
• the cured product of the thermally conductive composition of the present embodiment has a hardness increase rate calculated from the following formula (ii) of preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less. is. It is excellent in heat resistance in the said hardness increase rate being 50% or less.
• Hardness increase rate (%) (S A ⁇ S 0 )/S 0 ⁇ 100 (ii) (In the formula, S0 is the initial hardness of the test piece made of the cured product of the thermally conductive composition, and S A is the hardness of the test piece after exposure at a temperature of 130°C or 200°C for 168 hours.)
• the thermally conductive composition contains silicone as a polymer component
• a test piece made of a cured product of the thermally conductive composition is exposed at a temperature of 200 ° C. for 168 hours.
• a test piece made of the cured product of the thermally conductive composition is exposed at a temperature of 130° C. for 168 hours.
• the hardness increase rate can be specifically measured by the method described in Examples.
• the cured product of the thermally conductive composition of the present embodiment has a hardness reduction rate calculated from the following formula (iii) of preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. is. When the hardness reduction rate is 30% or less, the hydrolysis resistance is excellent.
• Hardness reduction rate (%) (S B ⁇ S 0 )/S 0 ⁇ 100 (iii) (In the formula, S0 is the initial hardness of the test piece made of the cured product of the thermally conductive composition, and SB is the hardness of the test piece after the PCT test.)
• the PCT test pressure cooker test
• the hardness reduction rate can be specifically measured by the method described in Examples.
• ⁇ Filler 1 (alumina): AES-12, manufactured by Sumitomo Chemical Co., Ltd., average particle size: 0.5 ⁇ m, specific surface area (BET method): 5.8 m 2 /g, thermal conductivity: 25 W/m ⁇ K ⁇ Filler 2 (alumina): BAK-5, manufactured by Shanghai Hyakuto Co., Ltd., average particle size: 5 ⁇ m, specific surface area (BET method): 0.4 m 2 /g, thermal conductivity: 25 W/m ⁇ K Filler 3 (alumina): Alumina AL45H, manufactured by Showa Denko KK, average particle size: 3.0 ⁇ m, specific surface area (BET method): 1.2 m 2 /g, thermal conductivity: 25 W/m ⁇ K ⁇ Filler 4 (alumina): Alnabeads (registered trademark) CB-A70, manufactured by Showa Denko KK, average particle size: 70 ⁇ m, specific surface area (BET method): 0.1 m 2
• ⁇ Filler 5 rounded alumina AS-05, manufactured by Showa Denko K.K., average particle size: 45 ⁇ m
• specific surface area BET method: 0.5 m 2 /g
• thermal conductivity 25 W/m ⁇ K
• ⁇ Filler 6 alumina: Alnabeads (registered trademark) CB-A100S, manufactured by Showa Denko KK, average particle diameter: 95 ⁇ m
• specific surface area (BET method) 0.1 m 2 /g
• thermal conductivity 25 W / m ⁇ K.
• the average particle size, specific surface area, and thermal conductivity of fillers 1 to 6 were measured by the following measuring methods.
• Polyurethane (polyadduct of castor oil-based polyol 1 and polyisocyanate compound 1 below)
• Castor oil-based polyol 1 manufactured by Ito Oil Co., Ltd., hydroxyl value: 23.2 mgKOH/g, acid value: 3.3 mgKOH/g, viscosity at 25°C: 78 mPa s, water content: 0.01% or less, number of hydroxyl groups: 2
• Polyisocyanate compound 1 URIC N-2023 (isocyanate-terminated prepolymer), manufactured by Ito Oil Co., Ltd., viscosity at 25 ° C.: 2290 mPa s, NCO content: 16% by mass
• the hydroxyl value of castor oil-based polyol 1 was measured according to JIS K0070:1992.
• the thermal conductivity of the polyurethane obtained from castor oil-based polyol 1 and polyisocyanate compound 1 is 0.3 W/m ⁇ K.
• Trimethoxysilyl group-containing polyurethane 1 SPUR+ 3030 PREPOLYMER, manufactured by Momentive Performance Materials Japan LLC, viscosity at 25°C: 2500 mPa ⁇ s, thermal conductivity: 0.3 W/m ⁇ K
• Viscosity The viscosity of the polymer component is measured at 25° C. using a rotational viscometer (manufactured by Toki Sangyo Co., Ltd., product name: TVB-10) based on JIS Z8803:2011 “Method for measuring viscosity of liquid”. bottom.
• Thermal conductivity of the polymer component was measured according to ISO 22007-2 using a hot disk thermophysical property measuring device (trade name: TPS 2500 S, manufactured by Kyoto Electronics Industry Co., Ltd.).
• ⁇ Silane coupling agent 1 KBM-3063 (trimethoxyhexylsilane), manufactured by Shin-Etsu Chemical Co., Ltd.
• ⁇ Silane coupling agent 2 KBM-3103C (decyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd.
• ⁇ Metal complex 1 TC-750 (titanium ethyl acetoacetate), Matsumoto Fine Chemical Co., Ltd.
• Dispersant 1 EXP6496D (polyester compound), manufactured by DIC Corporation Plasticizer 1: Licksizer C-401 (fatty acid ester derived from castor oil), Ito Oil Co., Ltd., viscosity at 25 ° C.: 20 mPa s
• the filler was surface-treated by the following surface treatments 1 to 15. Since hydrogen gas is generated during the reaction between the siloxane compound and the hydroxyl groups on the surface of the filler, safety measures such as releasing the generated hydrogen gas through an open valve attached to the stainless container were taken during the operation.
• filler 1 was heated in a hot air circulating oven at a temperature of 120° C. for 2 hours and then cooled to obtain a filler surface-treated by a direct method using decyltrimethoxysilane.
• the introduction rate of the siloxane-based group and the introduction rate of the decyl group or the group represented by formula (1) were in accordance with JIS R1675: 2007 "combustion (high-frequency heating) - infrared absorption method”. method.
• the total carbon content of the filler (original powder), the total carbon content of the filler surface-treated by chemical vapor deposition using siloxane, and the total carbon content of the filler into which a decyl group or a group represented by formula (1) has been introduced. were measured respectively.
• the ratio of introduction of groups based on siloxane was calculated from the value obtained by subtracting the total carbon content of the raw powder from the total carbon content of the filler surface-treated by chemical vapor deposition using siloxane.
• the total carbon content of the filler surface-treated by chemical vapor deposition using siloxane and the total carbon content of the raw powder were subtracted from the total carbon content of the filler into which the decyl group or the group represented by formula (1) was introduced.
• the introduction rate of the decyl group or the group represented by formula (1) was calculated from the value.
• the carbon content (% by mass) of 1-decene is 85.62
• the carbon content (% by mass) of ethoxy-diethylene glycol acrylate is 57.43.
• Example 1 Addition type silicone 1 6.25% by mass is added to a rotation / revolution mixing mixer (manufactured by Thinky Co., Ltd., product name: ARV-310P), and further, filler 1 (surface treatment 1) 18.75% by mass, filler 2 ( Surface treatment 2) 25.00% by mass and 50.00% by mass of filler 4 were added and defoamed and stirred for 30 seconds at a rotation speed of 2000 rpm to obtain a thermally conductive composition of Example 1.
• a rotation / revolution mixing mixer manufactured by Thinky Co., Ltd., product name: ARV-310P
• Example 2 and Comparative Examples 1 to 4 Thermally conductive compositions of Examples and Comparative Examples were obtained in the same manner as in Example 1, except that the components were changed to the types and blending amounts shown in Table 1.
• Example 3 Condensed silicone 1 8.43% by mass, filler 3 (surface treatment 11) 45.53% by mass, and filler 5 45.53% by mass are placed in a container and dried in an oven at a temperature of 100 ° C. for 30 minutes. The mixture was stirred for 30 seconds at a rotation speed of 2000 rpm with a rotation/revolution mixer (trade name: ARV-310P, manufactured by THINKY Co., Ltd.). After cooling to room temperature (25° C.), 0.34% by mass of silane coupling agent 1 was added and stirred for 30 seconds at 2000 rpm in a rotation/revolution mixing mixer. Further, 0.17% by mass of metal complex 1 was added, and defoaming and stirring was performed for 30 seconds at 2000 rpm in a rotation/revolution mixing mixer to obtain a thermally conductive composition of Example 3.
• a rotation/revolution mixer trade name: ARV-310P, manufactured by THINKY Co., Ltd.
• Example 4 and 5 and Comparative Examples 5 and 6 Thermally conductive compositions of Examples and Comparative Examples were obtained in the same manner as in Example 3, except that the components were changed to the types and blending amounts shown in Table 2.
• Example 6 8.01% by mass of castor oil-based polyol, 0.43% by mass of dispersant 1, 45.26% by mass of filler 3 (surface treatment 11), and 45.26% by mass of filler 5 were placed in a container and heated at 100°C for 30 minutes. After drying in an oven for 1 minute, it was stirred for 30 seconds at 2000 rpm with a rotation/revolution mixing mixer (trade name: ARV-310P, manufactured by Thinky Co., Ltd.). After cooling to room temperature (25 ° C.), 1.04% by mass of polyisocyanate compound 1 was added, and immediately degassed and stirred for 30 seconds at a rotation speed of 2000 rpm in a rotation / revolution mixing mixer. A sexual composition was obtained.
• a rotation/revolution mixing mixer trade name: ARV-310P, manufactured by Thinky Co., Ltd.
• Example 7 to 9 and Comparative Examples 7 and 8 Thermally conductive compositions of Examples and Comparative Examples were obtained in the same manner as in Example 6, except that the components were changed to the types and blending amounts shown in Table 3.
• Example 10 Trimethoxysilyl group-containing urethane 1 2.72% by mass, plasticizer 1 6.34% by mass, dispersant 1 0.18% by mass, filler 3 (surface treatment 11) 45.31% by mass, and filler 6 45.31% by mass After drying in an oven at a temperature of 100° C. for 30 minutes, it was stirred for 30 seconds at a rotation speed of 2000 rpm with a rotation/revolution mixer (manufactured by Thinky Co., Ltd., trade name: ARV-310P). After cooling to room temperature (25 ° C.), 0.14% by mass of metal complex 1 was added, and the mixture was defoamed and stirred for 30 seconds at a rotation speed of 2000 rpm in a rotation/revolution mixing mixer. got stuff
• Example 11 to 13 and Comparative Examples 9 and 10 Thermally conductive compositions of Examples and Comparative Examples were obtained in the same manner as in Example 10, except that the types and amounts of the components shown in Table 4 were changed.
• a sheet of This sheet was cut into strips having a width of 20 mm, and three strips were stacked to form a test piece (length 80 mm, width 20 mm, thickness 6 mm) for each example and comparative example.
• the thermally conductive composition of Comparative Example 4 was not cured and could not be peeled off from the 0.1 mm thick polyester film to which the fluorine release treatment was applied.
• thermoly conductive compositions of Examples 3 to 5 and Comparative Examples 5 and 6 A polyester film having a thickness of 0.1 mm subjected to fluorine release treatment was prepared, and a mold having a diameter of 45 mm and a thickness of 6 mm was prepared. put inside. Pour the defoamed thermally conductive composition into it so as not to let air in, flatten the surface with a spatula, and then leave it in a constant temperature room with a temperature of 23 ⁇ 2 ° C and a humidity of 50 ⁇ 10% RH for 1 week, A test piece (diameter: 45 mm, thickness: 6 mm) was obtained for each example and comparative example.
• thermally conductive compositions of Examples 6 to 13 and Comparative Examples 7 to 10 A defoamed thermally conductive composition was placed in a silicone mold (diameter 50 mm, depth 30 mm, 6 pieces). Pour to a height of 8 mm so that air does not enter, leave in a constant temperature room with a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 10% RH for 1 week, and test pieces (diameter 50 mm, thickness 8 mm) of each example and comparative example Obtained. The thermally conductive composition of Comparative Example 8 was not cured and could not be removed from the silicone mold.
• Viscosity The viscosity of the thermally conductive composition was measured in accordance with JIS K7210: 2014 using a flow viscometer (GFT-100EX, manufactured by Shimadzu Corporation) at a temperature of 30°C and a die hole diameter (diameter ) was measured under the conditions of 1.0 mm and a test force of 40 (weight of 7.8 kg).
• thermophysical property measuring device manufactured by Kyoto Electronics Industry Co., Ltd., trade name: TPS 2500 S.
• each specimen was then exposed in a hot air circulating oven at a temperature of 200° C. for 168 hours. After the exposure, the specimen was taken out and cooled at room temperature (23°C) for one day.
• the Asker A hardness of the test piece after the exposure was measured by the same operation as the measurement of the Asker A hardness in (2) above.
• the hardness increase rate was calculated from the following formula (ii). [Test piece in Table 4] For each test piece in Table 4, the Asker A hardness measured in (2) above is used as the initial hardness.
• Each specimen was then exposed in a hot air circulating oven at a temperature of 130° C. for 168 hours. After the exposure, the specimen was taken out and cooled at room temperature (23°C) for one day.
• the Asker A hardness of the test piece after the exposure was measured by the same operation as the measurement of the Asker A hardness in (2) above.
• the hardness increase rate was calculated from the following formula (ii). It is judged that the smaller the hardness increase rate, the better the heat resistance.
• Hardness increase rate (%) (S A ⁇ S 0 )/S 0 ⁇ 100 (ii) (Wherein, S0 is the initial hardness of the test piece and S A is the hardness of the test piece after exposure.)
• Consistency is the penetration of a 1/4 cone described in JIS K2220: 2013, using an automatic penetration tester (manufactured by Rigosha, RPM-101) at a temperature of 23 ° C. It was measured.
• Tack-free time A polyester film having a thickness of 0.1 mm, which has been subjected to fluorine release treatment, is prepared and placed in a mold having a diameter of 45 mm and a thickness of 6 mm. Pour the degassed thermally conductive composition there so that no air enters, flatten the surface with a spatula, then place it in a constant temperature room with a temperature of 23 ⁇ 2 ° C and a humidity of 50 ⁇ 10% RH, and tack the surface. The time until the liquid disappeared was measured every 15 minutes or every 5 minutes. Note that the tack-free time is an index of quick-drying property and represents a measure of curability of the composition. A longer tack-free time indicates a slower reaction rate.
• Hardness reduction rate (%) (S B ⁇ S 0 )/S 0 ⁇ 100 (iii) (In the formula, S0 is the initial hardness of the test piece, and S B is the hardness of the test piece after the PCT test.)
• both the thermally conductive compositions of Example 1 and Example 2 containing the filler (A) or the filler (B) defined in claim 1 as a filler are comparisons containing only fillers without surface treatment as fillers. Low viscosity compared to the thermally conductive composition of Example 4.
• both the test pieces made of the thermally conductive compositions of Examples 1 and 2 have a high thermal conductivity of 4.0 W / m K or more, and a filler in which SiH groups remain on the surface as a filler Compared to the test pieces made of the thermally conductive compositions of Comparative Examples 1 and 2 containing, the initial hardness is low and has an appropriate hardness.
• the SiH groups remaining on the filler surface act as a cross-linking agent, resulting in high initial hardness.
• the test pieces made of the thermally conductive compositions of Examples 1 and 2 are both test pieces made of the thermally conductive composition of Comparative Example 3, which contains a filler surface-treated with decyltrimethoxysilane as a filler. Compared to , it has excellent resilience, low hardness increase rate, and excellent heat resistance.
• the thermally conductive compositions of Examples 1 and 2 have a longer pot life than the thermally conductive compositions of Comparative Examples 1 and 2, and can be molded. It can be said that it has speed.
• thermally conductive compositions of Examples 3 to 5 containing the filler (A) or the filler (B) defined in claim 1 as a filler has a high thermal conductivity of 2.80 W / m K or more, It has a consistency of 249 to 287 and moderate softness, a low hardness increase rate of 3.5 to 4.9%, and excellent heat resistance.
• all of the thermally conductive compositions of Examples 3 to 5 had a long tack-free time of 60 minutes and were cured, so it can be said that they have an appropriate reaction rate. Further, from Examples 4 and 5, it can be seen that the smaller the amount of decyl groups introduced to the surface of the filler, the less thixotropy and the higher the consistency.
• test pieces made of the thermally conductive compositions of Examples 3 to 5 all had an Asker A hardness of 85 or less, indicating a moderate hardness.
• Comparative Example 5 which contains only a filler that has not been surface-treated as a filler, has a high consistency of 301 and a long tack-free time of 60 minutes, but has an Asker A hardness of 90, compared to Examples 3 to 5. I know it's hard.
• Comparative Example 6 which contains a filler surface-treated with decyltrimethoxysilane as a filler has a smaller consistency, a much faster tack-free time, and a higher Asker A hardness than those of Examples 3 to 5. I know it's hard.
• thermally conductive compositions of Examples 6 to 9 using the filler containing the filler (A) or the filler (B) defined in claim 1 has a high thermal conductivity of 2.70 W / m K or more. Also, as compared with the thermally conductive composition of Comparative Example 7, which uses only the filler that has not been surface-treated as the filler, the consistency is large, the hardness is low, and the hardness is moderate. Furthermore, the thermally conductive compositions of Examples 6 to 9 have a longer tack-free time than the thermally conductive composition of Comparative Example 7, and are cured, so it can be said that they have an appropriate reaction rate. It can be seen that the treatment to 1 does not affect the reaction rate. On the other hand, the thermally conductive composition of Comparative Example 8, which contained a filler surface-treated with decyltrimethoxysilane as a filler, had a high consistency but did not cure.
• Each of the thermally conductive compositions of Examples 10 to 13 using the filler containing the filler (A) or the filler (B) defined in claim 1 has a high thermal conductivity of 2.90 W / m K or more. Also, the consistency is greater than that of the thermally conductive composition of Comparative Example 9, which uses only fillers that have not been surface-treated as fillers.
• the cured products of the thermally conductive compositions of Examples 10 to 13 have improved heat resistance because the rate of hardness increase is small compared to the cured products of the thermally conductive compositions of Comparative Examples 9 and 10. I know there is.
• the cured products of the thermally conductive compositions of Examples 10 to 13 had a smaller hardness reduction rate than the cured products of the thermally conductive compositions of Comparative Examples 9 and 10. It can be seen that the quality is improved. Furthermore, the thermally conductive compositions of Examples 10 to 13 have a longer tack-free time than the thermally conductive composition of Comparative Example 9, and are cured, so it can be said that they have an appropriate reaction rate. It can be seen that the treatment to 1 does not affect the reaction rate.

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