WO2022191308A1 - 熱伝導性シート - Google Patents

熱伝導性シート Download PDF

Info

Publication number
WO2022191308A1
WO2022191308A1 PCT/JP2022/010800 JP2022010800W WO2022191308A1 WO 2022191308 A1 WO2022191308 A1 WO 2022191308A1 JP 2022010800 W JP2022010800 W JP 2022010800W WO 2022191308 A1 WO2022191308 A1 WO 2022191308A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermally conductive
conductive sheet
mass
titanium oxide
titanium nitride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/010800
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
裕介 春名
宏 田島
滋和 梅村
花乃絵 小松
友 飯原
淳一 木下
靖 岩井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tatsuta Electric Wire and Cable Co Ltd
Original Assignee
Tatsuta Electric Wire and Cable Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tatsuta Electric Wire and Cable Co Ltd filed Critical Tatsuta Electric Wire and Cable Co Ltd
Priority to US18/549,960 priority Critical patent/US20240150638A1/en
Priority to CN202280003650.4A priority patent/CN115397945A/zh
Priority to JP2022543175A priority patent/JP7153828B1/ja
Priority to KR1020227029127A priority patent/KR102843818B1/ko
Publication of WO2022191308A1 publication Critical patent/WO2022191308A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/30—Oxides other than silica
    • C04B14/303—Alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/30—Oxides other than silica
    • C04B14/305—Titanium oxide, e.g. titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/32—Carbides; Nitrides; Borides ; Silicides
    • C04B14/325—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/32—Carbides; Nitrides; Borides ; Silicides
    • C04B14/325—Nitrides
    • C04B14/326—Aluminium nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/30—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Other silicon-containing organic compounds; Boron-organic compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/10—Arrangements for heating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/20—Arrangements for cooling
    • H10W40/25—Arrangements for cooling characterised by their materials
    • H10W40/251—Organics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00465—Heat conducting materials
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with 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
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to thermally conductive sheets.
  • thermally conductive sheet (radiation sheet) is installed, for example, between a heat-generating component and a heat-radiating fin or metal plate, and is tightly attached to the heat-generating component by crimping without any gaps.
  • the generated heat can be transferred to heat radiating fins or the like to dissipate heat from the entire system.
  • the thermally conductive sheet is composed of, for example, a thermally conductive inorganic filler and a resin.
  • a thermally conductive inorganic filler inexpensive aluminum hydroxide, aluminum oxide (alumina), silicon carbide, boron nitride, aluminum nitride, etc., which are expected to have higher thermal conductivity, are used.
  • the resin for example, an acrylic resin or a urethane resin is used.
  • thermally conductive sheet those disclosed in Patent Documents 1 to 3, for example, are known.
  • thermally conductive sheets have been required to have even higher functionality, and those with better thermal conductivity than ever before are in demand.
  • a thermally conductive filler such as alumina or aluminum hydroxide.
  • carbon black which is widely used as a black colorant.
  • the addition of carbon black imparts electrical conductivity to the thermally conductive sheet, increases the dielectric constant, and impairs the insulating properties. Therefore, there is a demand for a thermally conductive sheet that has excellent thermal conductivity, insulating properties, a low dielectric constant, and excellent design.
  • the present disclosure has been made in view of the above, and an object of the present disclosure is to provide a thermally conductive sheet having excellent thermal conductivity, insulating properties, a low dielectric constant, and excellent design. be.
  • the inventors of the present disclosure have made intensive studies to achieve the above object, and found that the binder component, titanium oxide, titanium nitride, and other thermally conductive fillers are included, and the ratio of titanium oxide to the total of titanium oxide and titanium nitride is It has been found that by setting the ratio within a specific range, it has excellent thermal conductivity, insulating properties, a low dielectric constant, and excellent design.
  • the present disclosure relates to what was completed based on these findings.
  • the present disclosure includes binder components, titanium oxide, titanium nitride, and other thermally conductive fillers, A thermally conductive sheet is provided in which the ratio of titanium oxide to the total of titanium oxide and titanium nitride is 20-90% by mass.
  • the L * value of the surface of the thermally conductive sheet in the L * a * b * color system is preferably 41 or less.
  • the total content of titanium oxide and titanium nitride is preferably 0.3 to 10.0 parts by mass with respect to 100 parts by mass of the thermally conductive filler.
  • the total content of the thermally conductive filler, titanium oxide, and titanium nitride is preferably 70 to 100% by mass with respect to the total amount of the thermally conductive sheet.
  • the binder component preferably contains a silicone resin.
  • the dielectric constant of the thermally conductive sheet is preferably 15.0 or less.
  • the thermal conductivity of the thermally conductive sheet in the plane direction is preferably 4.8 W/mK or more.
  • the median diameter of titanium oxide and titanium nitride is preferably 15 nm or more.
  • the thermally conductive filler preferably contains alumina, or alumina and aluminum nitride.
  • the thermally conductive sheet of the present disclosure has excellent thermal conductivity, insulating properties, a low dielectric constant, and excellent design.
  • thermally conductive sheet (heat dissipation sheet) according to an embodiment of the present disclosure includes at least a binder component, titanium oxide, titanium nitride, and other thermally conductive fillers.
  • the thermally conductive sheet may be in a form without a substrate (substrate layer), a so-called “substrate-less”, or may be a thermally conductive sheet provided on at least one side of the substrate. good.
  • base material base material layer
  • the thermally conductive sheet may have a release sheet.
  • the release sheet may be provided on only one side of the thermally conductive sheet, or may be provided on both sides.
  • Examples of the release sheet include a film formed from a low-adhesive resin, a sheet including a substrate and a release treatment layer provided on at least one surface of the substrate, and the like. The release sheet is peeled off and removed when the thermally conductive sheet is used.
  • FIG. 1 is a cross-sectional schematic diagram showing one embodiment of the thermally conductive sheet of the present disclosure.
  • the thermally conductive sheet 1 includes a binder component 11 as a matrix component, thermally conductive fillers 12 dispersed in the binder component 11, and a black colorant 13 containing titanium oxide and titanium nitride. including.
  • a release sheet 2 and a release sheet 3 are provided on both sides of the thermally conductive sheet 1 , and the thermally conductive sheet 1 is sandwiched between the two release sheets 2 and 3 .
  • the binder component is a component that forms the matrix of the thermally conductive sheet.
  • the binder component include resins (binder resins) such as thermoplastic resins, thermosetting resins, and active energy ray-curable resins. Only one type of the binder component may be used, or two or more types may be used.
  • thermoplastic resin examples include polystyrene-based resin, vinyl acetate-based resin, polyester-based resin, polyolefin-based resin (e.g., polyethylene-based resin, polypropylene-based resin composition, etc.), polyimide-based resin, acrylic-based resin, and the like. be done. Only one type of the thermoplastic resin may be used, or two or more types may be used.
  • thermosetting resin examples include both resins having thermosetting properties (thermosetting resins) and resins obtained by curing the above thermosetting resins.
  • thermosetting resins examples include silicone resins, phenolic resins, epoxy resins, urethane resins, urethane urea resins, melamine resins, alkyd resins, polyimide resins, and acrylic resins. Only one kind of the thermosetting resin may be used, or two or more kinds thereof may be used.
  • the active energy ray-curable resin includes both a resin that can be cured by irradiation with an active energy ray (active energy ray-curable resin) and a resin obtained by curing the active energy ray-curable resin.
  • active energy ray-curable resin is not particularly limited, for example, a polymer of a polymerizable compound having at least two (meth)acryloyloxy groups in the molecule can be used. Only one type of the active energy ray-curable resin may be used, or two or more types may be used.
  • the binder resin is preferably a thermosetting resin, and more preferably a silicone resin from the viewpoint of excellent thermal conductivity, heat resistance, and insulation.
  • a silicone resin that is used for known or commonly used thermally conductive sheets can be used.
  • the silicone resin is preferably a two-liquid curing silicone resin from the viewpoint that the thermally conductive filler can be well dispersed without using a solvent. Only one type of the silicone resin may be used, or two or more types may be used.
  • the content of the binder component is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and still more preferably 5.0% by mass or more with respect to 100% by mass of the total amount of the thermally conductive sheet. is.
  • the content is 1.0% by mass or more, the thermally conductive sheet is less likely to become brittle, and the thermally conductive sheet has excellent film formability.
  • the above content is preferably 20.0% by mass or less, more preferably 15.0% by mass or less. In particular, it is preferable that the content of the silicone resin is within the above range.
  • Titanium oxide and titanium nitride can act as a black coloring agent in the thermally conductive sheet to improve the design, and can also act as a thermally conductive filler. Furthermore, since titanium oxide and titanium nitride do not have electrical conductivity, the design can be improved without imparting electrical conductivity to the thermally conductive sheet. Only one kind of titanium oxide and titanium nitride may be used, or two or more kinds thereof may be used.
  • the titanium oxide and titanium nitride contained in the thermally conductive sheet are particles. Titanium oxide and titanium nitride are blended as independent particles in the thermally conductive sheet. In addition, titanium oxide and titanium nitride may be surface-treated, but from the viewpoint of ensuring insulation and design, it is preferable not to have a shell layer (core-shell structure) or a surface treatment layer such as a surface treatment agent. preferable.
  • the median diameter of titanium oxide and titanium nitride is preferably 15 nm or more, more preferably 25 nm or more, still more preferably 40 nm or more, and particularly preferably 50 nm or more. When the median diameter is 15 nm or more, the dielectric constant becomes lower.
  • the median diameter is, for example, 100 nm or less, preferably 80 nm or less.
  • the median diameter is the median diameter in the particle size distribution of the mixture of titanium oxide and titanium nitride.
  • the median diameter is a median diameter (D50) measured by a dynamic light scattering method.
  • the ratio of titanium oxide to the total (100% by mass) of titanium oxide and titanium nitride is 20 to 90% by mass, preferably 30 to 80% by mass, more preferably 35 to 55% by mass. When the ratio is within the above range, the thermally conductive sheet can be sufficiently blackened, and the design is excellent.
  • the total content of titanium oxide and titanium nitride in the thermally conductive sheet is preferably 0.3 to 10.0 parts by mass, more preferably 0.3 to 10.0 parts by mass with respect to 100 parts by mass of the thermally conductive filler. is 0.5 to 9.0 parts by mass, more preferably 1.0 to 5.0 parts by mass, particularly preferably 1.2 to 2.0 parts by mass.
  • the thermally conductive sheet can be sufficiently blackened, and the design is excellent.
  • the content is 10.0 parts by mass or less, a sufficient amount of the thermally conductive filler can be blended, resulting in excellent thermal conductivity and excellent film formability of the thermally conductive sheet.
  • the thermally conductive filler is particles having thermal conductivity other than titanium oxide and titanium nitride, and is a component that exhibits thermal conductivity in the thermally conductive sheet.
  • the thermally conductive filler include metal particles; metal oxides such as alumina (aluminum oxide) and zinc oxide; nitrides such as aluminum nitride and boron nitride; metal hydroxides such as aluminum hydroxide; carbides; glass, silica, silicon carbide, silicon compounds such as silicon (silicon); ceramic fillers; inorganic fillers such as carbon materials such as carbon fibers, carbon nanotubes, and diamonds. Only one type of the thermally conductive filler may be used, or two or more types may be used.
  • the thermally conductive filler metal oxides and nitrides are preferable. Among them, it is more preferable to contain metal oxides. From the viewpoint of better thermal conductivity, it is preferable to contain both metal oxides and nitrides. Especially preferred. In particular, alumina is preferable as the metal oxide, and aluminum nitride and boron nitride are preferable as the nitride.
  • the thermally conductive filler contains a metal oxide and/or nitride, the content of the metal oxide and/or nitride in the thermally conductive filler is preferably 25% by mass or more, more preferably 30% by mass. % by mass or more.
  • the upper limit is not particularly limited, it is preferably 100% by mass or less.
  • the ratio of metal oxides to the total of metal oxides and nitrides is preferably 20 to 90% by mass, more preferably 30 to 70% by mass, and even more preferably is 35 to 55% by mass.
  • the thermal conductivity of the thermally conductive sheet is much more excellent.
  • the metal oxide in particular, alumina preferably has two or more peak tops in the particle size distribution, more preferably two peak tops. Also, one having five peak tops may be used.
  • peak top A and peak top B peak tops
  • peak top B peak top B
  • peak top C to G peak top C
  • peak top D is in the range of more than 1 ⁇ m and 10 ⁇ m.
  • the peak top E is preferably in the range of more than 10 ⁇ m and 40 ⁇ m
  • the peak top F is preferably in the range of more than 40 ⁇ m and 60 ⁇ m
  • the peak top G is 60 ⁇ m and within the range of 100 ⁇ m. In this case, the filling property of the metal oxide in the thermally conductive sheet becomes higher, and the thermal conductivity is more excellent.
  • the nitride in particular, aluminum nitride
  • the nitride preferably has two or more peak tops in the particle size distribution, more preferably two peak tops.
  • One of the two or more peak tops is preferably within the range of 0.5 to 20 ⁇ m, and the other is preferably within the range of 30 to 80 ⁇ m. In this case, the filling property of the nitride in the thermally conductive sheet becomes higher, and the thermal conductivity is more excellent.
  • the shape of the thermally conductive filler is not particularly limited, and is spherical (including true spheres and elliptical spheres), flake-like (scale-like), dendritic, massive, flat, needle-like, amorphous (polyhedron), and the like. are mentioned. Among them, from the viewpoint of higher filling property in the thermally conductive sheet and more excellent thermal conductivity, when the thermally conductive filler is a metal oxide, it is spherical, and when it is a nitride, it is spherical and / or non-spherical. A fixed shape (polyhedron) is preferred.
  • spherical metal oxide for example, alumina beads CB series manufactured by Showa Denko KK can be used.
  • spherical nitride for example, the RFS series manufactured by Thrutek can be used.
  • amorphous (polyhedral) nitride for example, the SFS series manufactured by Thrutek can be used.
  • the thermally conductive filler may or may not be surface-treated.
  • a silane coupling agent is mentioned as a surface treatment agent which performs the said surface treatment.
  • the thermally conductive filler has good dispersibility in the binder component (especially silicone resin), which is the matrix of the thermally conductive sheet. Excellent. Only one kind of the silane coupling agent may be used, or two or more kinds thereof may be used.
  • silane coupling agent examples include ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, etc., other than alkoxy groups.
  • silane coupling agent having a functional group (functional group-containing silane coupling agent); silane coupling agent having no functional group other than an alkoxy group such as n-decyltrimethoxysilane (functional group-free silane coupling agent) etc.
  • a silane coupling agent containing no functional group is preferable, more preferably an alkoxy, from the viewpoint of good wettability with the thermally conductive filler and expected improvement in bulk strength and flexibility of the thermally conductive sheet.
  • the content ratio (total amount) of the thermally conductive filler in the thermally conductive sheet is preferably 70 to 98% by mass, more preferably 80 to 98% by mass, with respect to 100% by mass of the total amount of the thermally conductive sheet. 95% by mass.
  • the content is 70% by mass or more, the filling rate of the thermally conductive filler in the thermally conductive sheet is high, and the thermal conductivity is excellent.
  • the content is 98% by mass or less, the thermally conductive sheet is less likely to become brittle, and excellent film-forming properties are obtained when the thermally conductive sheet is produced.
  • the total content of the thermally conductive filler, titanium oxide, and titanium nitride in the thermally conductive sheet is preferably 70 to 98% by mass with respect to 100% by mass as the total amount of the thermally conductive sheet. , more preferably 75 to 96% by mass, still more preferably 85 to 95% by mass, and particularly preferably 90 to 94% by mass.
  • the content ratio is 70% by mass or more, the filling property of the filler in the thermally conductive sheet is higher, and the thermal conductivity and design are excellent.
  • the content is 98% by mass or less, the thermally conductive sheet is less likely to become brittle, and excellent film-forming properties are obtained when the thermally conductive sheet is produced.
  • the thermally conductive sheet may contain components other than the various components described above.
  • the other components include thixotropic agents, dispersants, curing agents, curing accelerators, curing retarders, slight tackifiers, plasticizers, flame retardants, antioxidants, stabilizers, titanium oxide and nitriding agents.
  • examples include coloring agents other than titanium.
  • the thermally conductive sheet contains other coloring agents such as a black coloring agent other than titanium oxide and titanium nitride from the viewpoints of having insulating properties and excellent low dielectric constant and from the viewpoint of suppressing inhibition of hardening of the binder component. preferably not. It should be noted that other coloring agents may be included as long as they do not impair the effects of the present invention. Examples of the other coloring agents include conductive coloring agents such as carbon black and carbon materials such as carbon nanotubes. Further, it is preferable not to include a colorant containing sulfur because it inhibits curing of the binder component.
  • the content of the other coloring agent is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 100 parts by mass in total of titanium oxide and titanium nitride. It is 1 part by mass or less.
  • the thickness of the thermally conductive sheet is, for example, 0.2 to 10 mm, preferably 0.3 to 5 mm.
  • the thermally conductive sheet can be produced with good film-forming properties even if it is thin, and is suitable for use in small portable electronic devices. It is 1.2 mm or less, more preferably 1 mm or less, and particularly preferably 0.5 mm or less.
  • the thermal conductivity of the thermally conductive sheet in the planar direction is preferably 4.8 W/mK or higher, more preferably 5.0 W/mK or higher.
  • the thermal conductivity is 4.8 W/mK or more, the thermal conductivity and the heat dissipation are excellent.
  • the thermal conductivity of the thermally conductive sheet in the thickness direction is preferably 2.5 W/mK or more, more preferably 2.6 W/mK or more. When the thermal conductivity is 2.5 W/mK or more, the thermal conductivity and heat dissipation in the thickness direction are excellent.
  • the thermally conductive sheet preferably has a dielectric constant of 15.0 or less, more preferably 10.0 or less, and even more preferably 9.0 or less.
  • the dielectric constant is, for example, 3.0 or higher.
  • the heat conductive sheet preferably has a dielectric loss tangent of 0.02 or less, more preferably 0.01 or less.
  • the dielectric loss tangent is 0.02 or less, transmission loss of high-frequency signals flowing through circuits of electronic devices such as arithmetic processing units can be suppressed.
  • the L * value of the surface of the thermally conductive sheet in the L * a * b * color system is preferably 41 or less, more preferably 40 or less, still more preferably 39 or less, and particularly preferably 38 or less.
  • the design of the thermally conductive sheet is more excellent.
  • the total emissivity of the thermally conductive sheet measured in accordance with JIS R 1693-2 in a wavelength range of 1700 nm to 5600 nm at a temperature of 80°C is preferably 40% or more, more preferably 45%. or more, more preferably 48% or more.
  • the total emissivity is 40% or more, the heat-dissipating property of the thermally-conductive sheet is excellent.
  • the method for forming the thermally conductive sheet is not particularly limited, and a known or commonly used method for forming a film or forming a molded body can be employed. Among them, roll-to-roll film formation is preferable from the viewpoint of continuous film formation and excellent productivity.
  • the thermally conductive sheet is formed by, for example, coating a composition containing the various components described above on the release-treated surface of a base material or a release sheet to form a coating layer, and then drying or curing by heating. It can be manufactured as a film. Heating may be performed in a state where a release-treated surface of a release sheet is further laminated on the coating layer.
  • the composition contains the binder component, titanium oxide, titanium nitride, and the thermally conductive filler. Titanium oxide, titanium nitride, and the thermally conductive filler may be mixed in advance and then mixed with the binder component, and titanium oxide, titanium nitride, the thermally conductive filler, and the binder component are mixed at the same time. You may The composition is preferably in the form of a paste containing no organic solvent.
  • the method for producing a sheet of the above composition is not particularly limited, and a known coating method such as a sandwich method in which a material is placed between release sheets coated with a release agent and laminated with a roll laminator, a hot press molding machine, an extruder, etc. Construction method can be adopted.
  • Example 1 Alumina (mixture of 23.9 parts by mass of spherical alumina with a median diameter of 45 ⁇ m and 17.5 parts by mass of spherical alumina with a median diameter of 10 ⁇ m) and aluminum nitride (34.6 parts by mass of spherical aluminum nitride with a median diameter of 55 ⁇ m and a polyhedron with a median diameter of 2 ⁇ m)
  • aluminum nitride 34.6 parts by mass of spherical aluminum nitride with a median diameter of 55 ⁇ m and a polyhedron with a median diameter of 2 ⁇ m
  • a mixture of 23.0 parts by mass of aluminum nitride) (mass ratio 58:42) and a mixture of titanium oxide and titanium nitride (mass ratio 40:60, median diameter: 20 nm) are mixed to form a particle composition 1 was produced.
  • the alumina and aluminum nitride are prepared in advance by adding 1 part by weight of a silane coupling agent (trade name "Z-6210", manufactured by Dow Toray Industries, Inc., n-decyltrimethoxysilane) to 100 parts by weight of the particles, and adding 1 part by weight of the solvent. By stirring and mixing inside, surface treatment is performed with a silane coupling agent.
  • the above particle composition 1 was mixed with a mixture of 1st part and 2nd part of a silicone resin (trade name “TSE-3062”, manufactured by Momentive) to prepare a resin paste.
  • the resin paste was placed between the release-treated surfaces of two release sheets and laminated using a roll laminator to produce a laminate of [release sheet/resin paste layer/release sheet]. Then, the laminate is heated at 70° C. for 30 minutes to thermally cure the resin paste layer, and the thermally conductive sheet (thickness thickness: 800 ⁇ m).
  • Examples 2-5 The heats of Examples 2 to 5 were prepared in the same manner as in Example 1 except that the mixture of titanium oxide and titanium nitride having the mass ratio of titanium oxide and titanium nitride and the median diameter of the mixture shown in Table 1 were used. A conductive sheet was produced.
  • Example 6 As alumina, 7.4 parts by mass of spherical alumina particles with a median diameter of 0.3 ⁇ m, 20.7 parts by mass of spherical alumina particles with a median diameter of 1.9 ⁇ m, 20.7 parts by mass of spherical alumina particles with a median diameter of 21 ⁇ m, and a median Using 93.2 parts by mass of a mixture of 17.8 parts by mass of spherical alumina particles with a diameter of 44 ⁇ m and 26.6 parts by mass of spherical alumina particles with a median diameter of 73 ⁇ m, titanium oxide, titanium nitride, and the amount of silicone resin blended A thermally conductive sheet of Example 6 was produced in the same manner as in Example 1, except that Table 1 was used and aluminum nitride was not used.
  • Comparative example 1 A thermally conductive sheet of Comparative Example 1 was produced in the same manner as in Example 1 except that titanium oxide alone (median diameter: 300 nm) was used instead of the mixture of titanium oxide and titanium nitride.
  • Comparative example 2 A thermally conductive sheet of Comparative Example 2 was produced in the same manner as in Example 1 except that titanium oxide alone (median diameter: 35 nm) was used instead of the mixture of titanium oxide and titanium nitride.
  • Comparative example 3 Example 1 except that the blending amounts of aluminum nitride and alumina were changed as shown in Table 1, and 1.0 parts by mass of thermal black was used instead of 1.4 parts by mass of the mixture of titanium oxide and titanium nitride.
  • a thermally conductive sheet of Comparative Example 3 was produced in the same manner.
  • Comparative example 4 Aluminum nitride, titanium oxide, and titanium nitride are not used, and 50.9 parts by mass of spherical alumina particles with a median diameter of 45 ⁇ m, 37 parts by mass of spherical alumina particles with a median diameter of 5 ⁇ m, and spherical alumina particles with a median diameter of 0.2 ⁇ m
  • a thermally conductive sheet of Comparative Example 4 was produced in the same manner as in Example 1 except that 92.5 parts by mass of the mixture with 4.6 parts by mass was used and the blending amounts were as shown in Table 1.
  • Reference example 1 As the thermally conductive sheet of Reference Example 1, the product name "Thermo-TransUTW" (manufactured by Widework Co., Ltd.) was used.
  • Reference example 2 As the thermally conductive sheet of Reference Example 2, the trade name "Conductive Thermal Pad for CPU Cooling” (manufactured by Fosa) was used.
  • Thermal conductivity A bulk body having a thickness of 1 mm or more is prepared by laminating thermally conductive sheets, and heat is measured by a laser flash method using a thermophysical property measuring device (trade name “TA35”, manufactured by Bethel Co., Ltd.). Diffusivity measurements were performed. Further, the specific heat of the thermally conductive sheet was measured at 25° C. by the DSC method using a differential scanning calorimeter (trade name “X-DSC7000”, manufactured by Hitachi High-Tech Science Co., Ltd.). Further, the specific gravity of the thermally conductive sheet was measured by an underwater replacement method using an electronic hydrometer (trade name “EW-300SG”, manufactured by Alpha Mirage Co., Ltd.). Then, the thermal conductivity was calculated by calculation using the thermal diffusivity, specific heat, and specific gravity obtained above. Note that the thermal conductivity was calculated both in the planar direction and the thickness direction.
  • the thermally conductive sheets of Examples have high thermal conductivity, excellent thermal conductivity, low dielectric constant, insulating properties, and sufficiently low L * value, which is excellent in design.
  • the dielectric loss tangent was low.
  • the total emissivity of the thermally conductive sheets of Examples was estimated to be 40% or more.
  • titanium nitride was not used as the black colorant (Comparative Examples 1 and 2)
  • the L * value was high and the design was poor.
  • thermal black was used as the black colorant (Comparative Example 3)
  • the thermal conductivity was low and the thermal conductivity was poor.
  • thermoelectricity and total emissivity were low, and the design and thermal conductivity were low. Poor conductivity.
  • the thermally conductive sheet of Reference Example 1 had a dielectric constant exceeding the measurement limit and had electrical conductivity, while the thermally conductive sheet of Reference Example 2 had a low thermal conductivity and was inferior in thermal conductivity.
  • the thermally conductive sheet of the present invention can be used for electronic components that require heat dissipation effect.
  • thermally conductive sheets 2 1 thermally conductive sheets 2, 3 release sheet 11 binder component 12 thermally conductive filler 13 black colorant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2022/010800 2021-03-12 2022-03-11 熱伝導性シート Ceased WO2022191308A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/549,960 US20240150638A1 (en) 2021-03-12 2022-03-11 Thermally Conductive Sheet
CN202280003650.4A CN115397945A (zh) 2021-03-12 2022-03-11 导热片
JP2022543175A JP7153828B1 (ja) 2021-03-12 2022-03-11 熱伝導性シート
KR1020227029127A KR102843818B1 (ko) 2021-03-12 2022-03-11 열전도성 시트

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-040096 2021-03-12
JP2021040096 2021-03-12

Publications (1)

Publication Number Publication Date
WO2022191308A1 true WO2022191308A1 (ja) 2022-09-15

Family

ID=83228152

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/010800 Ceased WO2022191308A1 (ja) 2021-03-12 2022-03-11 熱伝導性シート

Country Status (6)

Country Link
US (1) US20240150638A1 (https=)
JP (1) JP7153828B1 (https=)
KR (1) KR102843818B1 (https=)
CN (1) CN115397945A (https=)
TW (1) TWI868430B (https=)
WO (1) WO2022191308A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2024111496A1 (https=) * 2022-11-22 2024-05-30

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025221825A1 (en) * 2024-04-17 2025-10-23 Henkel Ag & Co. Kgaa Thermal interface materials

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003509578A (ja) * 1999-09-21 2003-03-11 サンーゴバン セラミックス アンド プラスティクス，インコーポレイティド 熱管理のための疎水性化合物における熱伝導性材料
US20090143522A1 (en) * 2007-12-04 2009-06-04 Sea-Fue Wang Thermally Conductive Silicone Composition
JP2012076421A (ja) * 2010-10-05 2012-04-19 Sumitomo Bakelite Co Ltd 接着体
JP2013225697A (ja) * 2013-07-12 2013-10-31 Micro Coatec Kk 熱伝導性電子回路基板およびそれを用いた電子機器ならびにその製造方法
US20150034858A1 (en) * 2012-04-17 2015-02-05 Chandrashekar Raman Thermally conductive polymer compositions to reduce molding cycle time

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5085050B2 (ja) 2006-04-06 2012-11-28 株式会社マイクロン 高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート用配合粒子、高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート、および、その製造方法
JP5089908B2 (ja) 2006-04-06 2012-12-05 株式会社マイクロン 高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート用配合粒子、高熱伝導性樹脂コンパウンド・高熱伝導性樹脂成形体・放熱シート、および、その製造方法
JP5345340B2 (ja) 2008-05-16 2013-11-20 新日鉄住金マテリアルズ株式会社 アルミナ配合粒子および樹脂成形体
WO2012018242A2 (ko) * 2010-08-05 2012-02-09 한화케미칼 주식회사 탄소소재를 이용한 고효율 방열도료 조성물
CN102134474B (zh) * 2010-12-29 2013-10-02 深圳市优宝惠新材料科技有限公司 导热硅脂组合物
JP6378533B2 (ja) * 2013-06-01 2018-08-22 日東電工株式会社 熱伝導性粘着シート
KR102509813B1 (ko) * 2018-12-25 2023-03-14 후지고분시고오교오가부시끼가이샤 열전도성 조성물 및 이것을 사용한 열전도성 시트

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003509578A (ja) * 1999-09-21 2003-03-11 サンーゴバン セラミックス アンド プラスティクス，インコーポレイティド 熱管理のための疎水性化合物における熱伝導性材料
US20090143522A1 (en) * 2007-12-04 2009-06-04 Sea-Fue Wang Thermally Conductive Silicone Composition
JP2012076421A (ja) * 2010-10-05 2012-04-19 Sumitomo Bakelite Co Ltd 接着体
US20150034858A1 (en) * 2012-04-17 2015-02-05 Chandrashekar Raman Thermally conductive polymer compositions to reduce molding cycle time
JP2013225697A (ja) * 2013-07-12 2013-10-31 Micro Coatec Kk 熱伝導性電子回路基板およびそれを用いた電子機器ならびにその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2024111496A1 (https=) * 2022-11-22 2024-05-30

Also Published As

Publication number Publication date
CN115397945A (zh) 2022-11-25
KR20230156884A (ko) 2023-11-15
JP7153828B1 (ja) 2022-10-14
JPWO2022191308A1 (https=) 2022-09-15
US20240150638A1 (en) 2024-05-09
KR102843818B1 (ko) 2025-08-07
TWI868430B (zh) 2025-01-01
TW202248398A (zh) 2022-12-16

Similar Documents

Publication Publication Date Title
CN104748606B (zh) 冷却结构体
TWI700243B (zh) 六方晶氮化硼粉末及其製造方法以及使用其之組成物及散熱材
US20210332281A1 (en) Heat radiation material, method for producing heat radiation material, heat radiation material kit, and heat generator
JP6023474B2 (ja) 熱伝導性絶縁シート、金属ベース基板及び回路基板、及びその製造方法
KR101784148B1 (ko) 열전도성 에폭시 복합조성물, 이의 제조방법 및 열전도 기능성 접착제
JP7153828B1 (ja) 熱伝導性シート
CN110546209B (zh) 树脂材料、树脂材料的制造方法及叠层体
CN104559819B (zh) 一种高性能纳米碳散热复合材料
KR20180084095A (ko) 방열기, 전자 기기, 조명 기기 및 방열기의 제조 방법
JP2022180564A (ja) 熱硬化性シート及び硬化シートの製造方法
TW201826465A (zh) 熱傳導片及半導體裝置
JPWO2008075574A1 (ja) 放熱材
KR101531630B1 (ko) 초박막 방열필름 및 이를 포함하는 열확산 시트
CN109177382A (zh) 一种高导热高散热性挠性覆铜板及其制备方法
KR20170123394A (ko) 방열 특성이 향상된 코팅 조성물 및 이를 이용한 도막의 형성 방법
CN105505334B (zh) 一种石墨烯散热体、制备方法及其应用
JP5495429B2 (ja) 放熱性複合シート
KR102653614B1 (ko) 방열 시트
WO2026075219A1 (ja) 熱伝導性シート
WO2025197773A1 (ja) 電磁波吸収熱伝導性シート
US10501628B2 (en) Resin composition, and electronic component and electronic device using same
JP2019089956A (ja) 樹脂組成物及び積層体
JP2026060329A (ja) 熱伝導性シート
JP2023107225A (ja) 積層体、及び半導体装置
CN108841284A (zh) 一种电气设备专用散热涂料及其制备方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2022543175

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22767262

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18549960

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22767262

Country of ref document: EP

Kind code of ref document: A1