WO2023090240A1 - Graisse de dissipation de chaleur - Google Patents

Graisse de dissipation de chaleur Download PDF

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Publication number
WO2023090240A1
WO2023090240A1 PCT/JP2022/041845 JP2022041845W WO2023090240A1 WO 2023090240 A1 WO2023090240 A1 WO 2023090240A1 JP 2022041845 W JP2022041845 W JP 2022041845W WO 2023090240 A1 WO2023090240 A1 WO 2023090240A1
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WIPO (PCT)
Prior art keywords
meth
thermally conductive
grease
unit
copolymer
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PCT/JP2022/041845
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English (en)
Japanese (ja)
Inventor
光祐 和田
健司 深尾
和宏 大島
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デンカ株式会社
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Priority to JP2023512336A priority Critical patent/JP7262699B1/ja
Publication of WO2023090240A1 publication Critical patent/WO2023090240A1/fr

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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

Definitions

  • the present invention relates to thermal grease.
  • a circuit board used in an on-board power supply system for an electric vehicle generally generates a large amount of heat due to a large voltage and current. An increase in the amount of heat generated causes circuit malfunctions and failures.
  • a battery pack that supplies power to an electric motor of an electric vehicle generates heat as it is repeatedly charged and discharged. Continuing to use the battery pack at a high temperature may reduce the performance and life of the battery pack.
  • heat generation problems are not limited to electric vehicles, but also occur in electronic devices.
  • the heat density inside electronic devices, which are becoming more sophisticated and smaller in size, is increasing year by year.
  • the heat-removing method is adopted by bringing the heat-generating part and the cooling member into contact. At this time, if there is a gap between the heat-generating member and the cooling member, the heat removal efficiency is reduced. Therefore, generally, the heat-generating portion and the cooling member are indirectly brought into contact with each other through a heat-dissipating member to remove the heat. .
  • heat dissipating members examples include heat dissipating grease.
  • the heat-dissipating grease is a paste obtained by kneading a thermally conductive filler and a liquid polymer. Since the heat dissipation grease has good wettability to the surface of the mounting member and has good conformability to microscopic unevenness, the contact thermal resistance can be reduced. Further, since the heat dissipating grease has fluidity, the grease layer can be thinned by crushing with pressure, so that the heat resistance of the grease layer can be reduced. Therefore, the heat-dissipating grease has high heat-conducting performance among the heat-dissipating members.
  • a heat-dissipating grease that uses boron nitride particles as a thermally conductive filler is known as a conventional technology (see Patent Document 1, for example). Since boron nitride particles have high thermal conductivity, the use of boron nitride particles as the thermally conductive filler can further enhance the thermal conductivity performance of the thermal grease.
  • thermally conductive filler when boron nitride particles are used as the thermally conductive filler, it becomes difficult to reduce the viscosity of the thermal grease, resulting in poor applicability of the thermal grease.
  • thermally conductive fillers other than boron nitride particles usually have a higher density than boron nitride particles. becomes higher. As a result, the electronic equipment using the thermal grease becomes heavy.
  • the use of such heat-dissipating grease makes the vehicle heavy and degrades the fuel efficiency of the vehicle.
  • an object of the present invention is to provide a heat-dissipating grease with a low specific gravity and a low viscosity.
  • the present inventors have made intensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using boron nitride particles surface-treated with a surfactant as a thermally conductive filler, and have completed the present invention. That is, the present invention is as follows. [1] A thermally conductive grease containing boron nitride particles and having a viscosity of 3000 Pa ⁇ s or less when measured at 25° C. and at a shear rate of 1 s ⁇ 1 . [2] The heat-dissipating grease according to [1] above, which contains a surfactant.
  • heat-dissipating grease with low specific gravity and low viscosity can be provided.
  • the (meth)acrylic monomer units of the present invention mean both methacrylic acid monomer units and acrylic monomer units.
  • the thermal grease of this embodiment contains boron nitride particles and has a viscosity of 3000 Pa ⁇ s or less when measured at 25° C. and at a shear rate of 1 s ⁇ 1 .
  • the thermally conductive filler used in the thermal grease of this embodiment contains boron nitride particles. If the thermally conductive filler used in the thermally conductive grease of the present embodiment does not contain boron nitride particles, it is difficult to achieve both a low specific gravity and a high thermal conductivity in the thermally conductive grease. From this point of view, the content of the boron nitride particles in the thermal grease of the present embodiment is preferably 20% by volume or more, more preferably 25% by volume or more, and still more preferably 35% by volume or more. . From the viewpoint of the applicability of the heat dissipating grease, the content of the boron nitride particles in the heat dissipating grease of the present embodiment is preferably 70% by volume or less, more preferably 60% by volume or less.
  • the boron nitride particles in the thermal grease of the present embodiment may contain massive boron nitride particles in which primary particles of hexagonal boron nitride are agglomerated. As a result, it is possible to improve the applicability of the thermal grease. Moreover, the boron nitride particles in the thermal grease of the present embodiment may further contain primary particles of non-agglomerated hexagonal boron nitride. As a result, the thermal grease can contain boron nitride particles at a higher density. Further, the boron nitride particles in the thermal grease of the present embodiment may be only non-aggregated primary particles of hexagonal boron nitride. As a result, the minimum film thickness of the thermal grease can be further reduced.
  • the thermally conductive filler used in the thermally conductive grease of this embodiment may contain thermally conductive fillers other than boron nitride particles.
  • Thermally conductive fillers other than boron nitride particles include, for example, one or more selected from aluminum nitride particles, aluminum oxide particles, silicon nitride particles, silicon oxide particles, magnesium oxide particles, metal aluminum particles, and zinc oxide particles. particles.
  • the content of the boron nitride particles in the thermally conductive filler is preferably 40-100% by volume, more preferably 55-100% by volume.
  • the average particle size of the thermally conductive filler is preferably 0.4-120 ⁇ m, more preferably 5-80 ⁇ m.
  • the average particle size of the thermally conductive filler is preferably 0.4-120 ⁇ m, more preferably 5-80 ⁇ m.
  • the thermally conductive filler may be a mixture of thermally conductive fillers having multiple average particle sizes. Compared to the case of containing only thermally conductive fillers having a single average particle size, the combined use of thermally conductive fillers having a smaller average particle size reduces the gaps between large-sized thermally conductive fillers. It can be filled with small diameter thermally conductive fillers. Therefore, by using a mixture of thermally conductive fillers having a plurality of average particle sizes, it becomes possible to fill the heat dissipating grease with the thermally conductive filler at a higher rate.
  • the thermally conductive filler is highly filled in this manner, the viscosity is remarkably increased, which may cause problems such as deterioration of coatability and uniform dispersion of the thermally conductive filler.
  • a surfactant such problems associated with high filling can be suppressed. And thereby, it becomes possible to further improve the thermal conductivity which improves according to the filling amount of the thermally conductive filler.
  • the content of the thermally conductive filler is preferably 25 to 75 parts by volume, more preferably 30 to 70 parts by volume, with respect to a total of 100 parts by volume of the thermally conductive filler and the liquid polymer described later. More preferably 35 to 65 parts by volume.
  • the content of the thermally conductive filler is 25 parts by volume or more, the thermal conductivity tends to be further improved.
  • the content of the thermally conductive filler is 75 parts by volume or less, the dispersibility of the thermally conductive filler in the heat dissipating grease is improved.
  • liquid polymer used in the thermal grease of the present embodiment is not particularly limited, but examples include hydrocarbon oils such as polyolefins, alkylaromatics and alicyclic compounds, polyglycols, polyethers such as phenyl ether, diesters, Examples include esters such as polyol esters, phosphorus compounds such as aromatic phosphate esters, silicon compounds such as silicone oils, halogen compounds such as fluorinated polyethers, mineral oils, fluorosilicone, acrylic resins, and urethane resins.
  • silicone oil is preferred from the viewpoint of heat resistance, weather resistance, electrical insulation and chemical stability.
  • the viscosity of the thermally conductive grease of this embodiment is 3000 Pa ⁇ s or less when measured at 25° C. and at a shear rate of 1 s ⁇ 1 . If the viscosity is greater than 3000 Pa ⁇ s when measured at 25° C. and at a shear rate of 1 s ⁇ 1 , the applicability of the thermal grease may deteriorate. From such a viewpoint, the viscosity of the thermally conductive grease of the present embodiment when measured at 25° C. and at a shear rate of 1 s ⁇ 1 is preferably 2000 Pa s or less, more preferably 1500 Pa s or less. .
  • the viscosity of the heat dissipating grease of the present embodiment when measured at 25° C. and at a shear rate of 1 s ⁇ 1 is preferably 50 Pa s or more, more preferably 200 Pa ⁇ s or more.
  • the viscosity of the thermal grease can be measured by the method described in Examples below.
  • the specific gravity of the thermal grease of this embodiment is preferably 2.0 or less.
  • the specific gravity of the heat-dissipating grease is 2.0 or less, the weight of the electronic device using the heat-dissipating grease can be reduced.
  • electronic devices for vehicles use a large amount of heat-dissipating grease, so the effect is greater.
  • the specific gravity of the heat-dissipating grease of the present embodiment is more preferably 2.0 or less, and still more preferably 1.8 or less.
  • the lower limit of the specific gravity range of the thermal grease of the present embodiment is not particularly limited, but is usually 1.3 or more.
  • the specific gravity of the thermal grease can be measured by the method described in Examples below.
  • the thermal conductivity of the thermal grease of this embodiment is preferably 1.0 W/m ⁇ K or more.
  • the heat conductivity of the heat dissipation grease is 1.0 W/m ⁇ K or more, the heat conductivity between the heat generating portion and the cooling member can be further improved.
  • the thermal conductivity of the heat dissipating grease of the present embodiment is more preferably 1.5 W/m ⁇ K or more, and still more preferably 2.0 W/m ⁇ K or more.
  • the upper limit of the thermal conductivity range of the thermal grease of the present embodiment is not particularly limited, but is usually 8 W/m ⁇ K or less.
  • the thermal conductivity of the thermal grease can be measured by the method described in Examples below.
  • the volume resistivity of the thermal grease of this embodiment is preferably 1 ⁇ 10 13 ⁇ cm or more.
  • the volume resistivity of the heat dissipation grease is 1 ⁇ 10 13 ⁇ cm or more, the insulation between the heat generating portion and the cooling member can be further improved.
  • the volume resistivity of the heat-dissipating grease of the present embodiment is more preferably 5 ⁇ 10 13 ⁇ cm ⁇ or more, and still more preferably 1 ⁇ 10 14 ⁇ cm or more.
  • the upper limit of the volume resistivity range of the thermal grease of the present embodiment is not particularly limited, but is usually 1 ⁇ 10 16 ⁇ cm or less.
  • the volume resistivity of the thermal grease can be measured by the method described in Examples below.
  • the film thickness of the thermal grease of this embodiment is preferably 120 ⁇ m or less.
  • the minimum film thickness of the heat-dissipating grease is 120 ⁇ m or less, the thermal resistance of the heat-dissipating grease layer formed between the heat-generating portion and the cooling member can be further reduced by the heat-dissipating grease.
  • the minimum film thickness of the thermal grease of the present embodiment is more preferably 100 ⁇ m or less, and still more preferably 75 ⁇ m or less.
  • the lower limit of the minimum film thickness range of the thermal grease of the present embodiment is not particularly limited, but is usually 2 ⁇ m or more.
  • the minimum film thickness of the thermal grease can be measured by the method described in Examples below.
  • the thermal grease of this embodiment preferably contains a surfactant.
  • a surfactant By including a surfactant in the thermally conductive grease, the viscosity of the thermally conductive grease can be further reduced.
  • the surfactant is used for the purpose of uniformly dispersing the thermally conductive filler in the liquid polymer.
  • the surfactant is not particularly limited as long as it can reduce the viscosity of the heat dissipating grease containing boron nitride particles, but a surfactant having an anionic group and a cationic group is preferable, and a surfactant containing a copolymer described later agents are more preferred.
  • the surfactant may further contain a solvent and other optional additives, if necessary.
  • Surfactants prevent agglomeration and sedimentation of thermally conductive fillers in thermal grease, improving the stability of thermally conductive fillers. Also, the viscosity of thermal grease can be reduced. In addition, it is possible to improve various effects associated with improvement in the dispersibility of the thermally conductive filler.
  • Surfactants can disperse the thermally conductive fillers by electrostatic repulsion and prevent the reaggregation of the thermally conductive fillers. Moreover, it is preferable that the surfactant further has an effect of improving dispersibility by steric hindrance repulsive force.
  • the copolymer used for the surfactant comprises a (meth)acrylic monomer unit A having an anionic group, a (meth)acrylic monomer unit B having a cationic group, and the (meth)acrylic It has a monomer unit A and a (meth)acrylic monomer unit C other than the (meth)acrylic monomer unit B, and the (meth)acrylic monomer unit C has a weight average molecular weight of 2 ,000 to 9,000.
  • the copolymer can significantly reduce the viscosity of the heat-dissipating grease. The reason is considered as follows.
  • a predetermined potential difference is generated at the interface where two different substances are in contact, such as the surface of a thermally conductive filler dispersed in a liquid polymer, attracting counterions and forming an electric double layer consisting of a stationary phase and a diffusion double layer.
  • the spread of counterions on the surface of the thermally conductive filler is also called the thickness of the electric double layer.
  • the thermally conductive fillers approach each other, the counter ions overlap and the electrostatic repulsion increases. It is believed that the copolymer has an amphoteric property of an anionic group and a cationic group in its molecule, thereby increasing the thickness of this electric double layer.
  • one of the anionic group and the cationic group of the copolymer is arranged near the surface of the thermally conductive filler as a counterion.
  • the other group (secondary ion) that does not function as a counter ion is located farther than the surface of the thermally conductive filler, where it can further form a secondary ion layer.
  • the term “monomer” refers to a monomer having a polymerizable unsaturated bond before polymerization
  • the term “monomer unit” refers to a repeating unit that constitutes a part of the copolymer after polymerization.
  • a unit derived from a given monomer is also simply referred to as “unit A”
  • “(meth)acrylic monomer unit B” is simply referred to as “unit B”
  • (Meth)acrylic monomer unit C” is also simply referred to as “unit C”.
  • the (meth)acrylic monomer unit A is a repeating unit having an anionic group.
  • anionic groups include, but are not limited to, carboxy groups, phosphoric acid groups, phenolic hydroxy groups, and sulfonic acid groups. Among these, one or more selected from the group consisting of a carboxy group, a phosphoric acid group, and a phenolic hydroxy group is preferable, and a carboxy group is more preferable. Having such a group tends to further improve the dispersibility of the thermally conductive filler. As a result, the viscosity of the thermal grease of this embodiment can be sufficiently reduced.
  • the unit A preferably further has an electron-withdrawing group bonded to the anionic group.
  • an electron-withdrawing group is not particularly limited as long as it has the effect of stabilizing the anion of the anionic group.
  • an acrylic monomer containing an electron-withdrawing substituent such as a halogen element on the ⁇ -position carbon atom of the carboxy group may be used. Having such a group tends to further improve the dispersibility of the thermally conductive filler. As a result, the viscosity of the thermal grease of this embodiment can be sufficiently reduced.
  • Unit A preferably does not have an electron-donating group bonded to an anionic group or has a group with low electron-donating property.
  • Such an electron-donating group is not particularly limited as long as it has the effect of destabilizing the anion of the anionic group.
  • an acrylic monomer that does not contain an electron-donating group substituent such as a methyl group on the ⁇ -position carbon atom of the carboxy group may be used.
  • Such a structure tends to further improve the dispersibility of the thermally conductive filler.
  • the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • Examples of such (meth)acrylic monomers include, but are not limited to, acrylic acid, methacrylic acid, acid phosphoxypropyl methacrylate, acid phosphoxypolyoxyethylene glycol monomethacrylate, acid phosphoxypoly Oxypropylene glycol monomethacrylate, phosphoric acid-modified epoxy acrylate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, 2-methacryloyloxyethyl succinic acid, 2 -acrylamido-2-methylpropanesulfonic acid and the like.
  • acrylic acid 2-methacryloyloxyethyl phosphate, 4-hydroxyphenyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid are preferred, and acrylic acid is more preferred.
  • the affinity of the copolymer for the thermally conductive filler tends to be further improved, and the dispersibility of the thermally conductive filler tends to be further improved.
  • the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • Unit A may be used singly or in combination of two or more.
  • the (meth)acrylic monomer unit B is a repeating unit having a cationic group.
  • the cationic group is not particularly limited, but for example, the cationic group is one or more selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium salts. is preferred. Among these, a tertiary amino group is more preferable. Having such a group tends to further improve the dispersibility of the thermally conductive filler. As a result, the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • the unit B preferably further has an electron-donating group bonded to the cationic group.
  • an electron-donating group is not particularly limited as long as it has the effect of stabilizing the cation of the cationic group.
  • an acrylic monomer containing an electron-donating substituent such as a methyl group on the ⁇ -position carbon atom of the amino group may be used. Having such a group tends to further improve the dispersibility of the thermally conductive filler. As a result, the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • Unit B preferably does not have an electron-withdrawing group bonded to a cationic group, or preferably has a group with low electron-withdrawing properties.
  • Such an electron-withdrawing group is not particularly limited as long as it has the effect of destabilizing the cation of the cationic group.
  • an acrylic monomer that does not contain an electron-withdrawing group substituent such as a carboxyl group on the ⁇ -position carbon atom of an amino group may be used.
  • Such a structure tends to further improve the dispersibility of the thermally conductive filler.
  • the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • Examples of such (meth)acrylic monomers include, but are not limited to, 1-aminoethyl acrylate, 1-aminopropyl acrylate, 1-aminoethyl methacrylate, 1-aminopropyl methacrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl methacrylate, t-butylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylate quaternary salt, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl- 4-piperidyl methacrylate, dimethylaminoethyl acrylate benzyl chloride quaternary salt and the like.
  • 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate are preferred, and 1,2,2,6,6- Pentamethyl-4-piperidyl methacrylate is more preferred.
  • Unit B may be used singly or in combination of two or more.
  • (Meth)acrylic monomer unit C) is a (meth)acrylic monomer unit other than unit A and unit B, and is a (meth)acrylic monomer unit containing no cationic or anionic group in the molecule. Quantity.
  • the (meth)acrylic monomer C preferably has a skeleton with high affinity or compatibility with the liquid polymer used in the heat-dissipating grease.
  • a skeleton is not particularly limited, but for example, an amphipathic skeleton such as an oxyalkylene skeleton, a siloxane skeleton such as dimethylsiloxane, a hydrophobic skeleton such as a hydrocarbon skeleton such as alkyl or aryl, or a phosphate diester skeleton. and other hydrophilic skeletons.
  • an oxyalkylene skeleton, a siloxane skeleton, and a hydrocarbon skeleton are preferred, a siloxane skeleton and a hydrocarbon skeleton are more preferred, and a siloxane skeleton is even more preferred.
  • Having such a skeleton tends to further improve the compatibility between the copolymer and the liquid polymer, and further improve the dispersibility of the thermally conductive filler in the heat dissipating grease.
  • the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • Examples of such (meth)acrylic monomers include, but are not limited to, ethoxycarbonylmethyl (meth)acrylate, phenol ethylene oxide-modified (meth)acrylate, phenol (ethylene oxide 2 mol modified) (meth)acrylate , phenol (modified by 4 moles of ethylene oxide) (meth)acrylate, paracumylphenol ethylene oxide-modified (meth)acrylate, nonylphenol ethylene oxide-modified (meth)acrylate, nonylphenol (modified by 4 moles of ethylene oxide) (meth)acrylate, nonylphenol (ethylene oxide 8 mol modified) (meth) acrylate, nonylphenol (propylene oxide 2.5 mol modified) acrylate, 2-ethylhexyl carbitol (meth) acrylate, ethylene oxide modified phthalic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) (meth)acrylic monomers having an oxyalkylene skeleton such as
  • (meth) Acrylic monomer 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (Meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate and other hydroxyl group-containing (meth)acrylic monomers; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide , N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylic monomer having an amide bond such as acryloylmorpholine; ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane (Meth) acrylic monomers having a siloxane skeleton such as; (meth) acrylic monomers having a phosphoric acid diester skeleton such
  • Unit C may be used singly or in combination of two or more.
  • (meth)acrylic monomers having a siloxane skeleton such as ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane are preferred.
  • the (meth)acrylic monomer C preferably has a weight average molecular weight of 2,000 to 9,000.
  • the copolymer has good affinity for the liquid polymer, and the dispersibility of the thermally conductive filler is further improved. As a result, the viscosity of the thermal grease of this embodiment can be sufficiently reduced.
  • the weight average molecular weight of the (meth)acrylic monomer C is 9,000 or less, the copolymer can be easily dissolved in the liquid polymer.
  • the weight average molecular weight of the (meth)acrylic monomer C is more preferably 2,500 to 7,000, still more preferably 3,000 to 6,000, and still more preferably 3,500 to 5,500.
  • the weight average molecular weight of the (meth)acrylic monomer C is the weight average molecular weight of the (meth)acrylic monomer unit C.
  • the content of unit A is preferably 30 to 80 mol%, more preferably 40 to 65 mol%, relative to the total 100 mol% of unit A, unit B, and unit C.
  • the content of the unit A is 30 mol % or more, the affinity of the copolymer to the liquid polymer tends to be further improved, and the dispersibility of the thermally conductive filler tends to be further improved.
  • the copolymer can sufficiently reduce the viscosity of the thermal grease of the present embodiment.
  • the content of the unit A is 80 mol % or less, the copolymer can contain the unit B and the unit C in sufficient content.
  • the content of unit B is preferably 0.1 to 5 mol%, more preferably 0.5 to 3 mol%, relative to the total 100 mol% of unit A, unit B, and unit C. preferable.
  • the content of the unit B is preferably 0.1 to 5 mol%, more preferably 0.5 to 3 mol%, relative to the total 100 mol% of unit A, unit B, and unit C. preferable.
  • the total content of unit A and unit B is preferably 30.1 to 85 mol%, preferably 35 to 75 mol%, relative to the total 100 mol% of unit A, unit B, and unit C. is more preferred.
  • the total content of the units A and B is 30.1 mol % or more, the affinity of the copolymer to the liquid polymer tends to be further improved, and the dispersibility of the thermally conductive filler tends to be further improved.
  • the unit C can be contained in the copolymer in a sufficient content.
  • the molar ratio of unit A to unit B is preferably 6-800, more preferably 20-400.
  • the affinity of the copolymer for the liquid polymer tends to be further improved, and the dispersibility of the thermally conductive filler tends to be further improved.
  • the content of unit C is preferably 20 to 70 mol%, more preferably 30 to 55 mol%, relative to the total 100 mol% of unit A, unit B, and unit C.
  • the content of unit C is preferably 20 to 70 mol%, more preferably 30 to 55 mol%, relative to the total 100 mol% of unit A, unit B, and unit C.
  • the weight average molecular weight of the copolymer is preferably 40,000 to 80,000, more preferably 50,000 to 70,000.
  • the weight-average molecular weight of the copolymer is 40,000 or more, the steric hindrance repulsive force of the copolymer makes it more difficult for the thermally conductive filler to aggregate, and the dispersibility of the thermally conductive filler in the heat dissipating grease is further improved. be improved.
  • the weight average molecular weight of the copolymer is 80,000 or less, it becomes easier to dissolve the copolymer in the liquid polymer.
  • the weight average molecular weight can be determined by GPC (gel permeation chromatography).
  • the copolymer is preferably a copolymer represented by the following general formula (1).
  • the copolymer represented by formula (1) may be a random copolymer or a block copolymer.
  • the unit A of the copolymer represented by the following general formula (1) is derived from acrylic acid, and the anionic group is a carboxy group.
  • the unit B of the copolymer represented by the following general formula (1) is derived from 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and the cationic group is a tertiary amino group. be.
  • the unit C of the copolymer represented by the following general formula (1) is derived from ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane and has a siloxane skeleton.
  • s is, when the weight average molecular weight of the copolymer is 40,000 to 80,000, the content of unit A is 30 to 30 to 100 mol% of the total of unit A, unit B, and unit C t is an integer such that it is 80 mol %, and t is the total content of unit A, unit B, and unit C when the weight average molecular weight of the copolymer is 40,000 to 80,000 is an integer such that it is 20 to 70 mol% with respect to 100 mol%, u is when the weight average molecular weight of the copolymer is 40,000 to 80,000, the content of unit B is unit A, It is an integer such that it is 0.1 to 5.0 mol % with respect to 100 mol % of the total of units B and C. Further, v is an integer such that the weight average molecular weight of unit C is 2,000 to 9,000.
  • the method for producing the above copolymer is not particularly limited, and a known polymerization method for (meth)acrylic monomers can be used.
  • Examples of the polymerization method include radical polymerization and anionic polymerization. Among these, radical polymerization is preferred.
  • the thermal polymerization initiator used for radical polymerization is not particularly limited, and examples thereof include azo compounds such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide and di-tert-butyl peroxide; things, etc.
  • the photopolymerization initiator used for radical polymerization is not particularly limited, but a benzoin derivative can be used.
  • known polymerization initiators used for living radical polymerization such as ATRP and RAFT can also be used.
  • the polymerization conditions are not particularly limited, and can be appropriately adjusted depending on the initiator used, the boiling point of the solvent, and the type of other monomers.
  • the order of addition of the monomers is not particularly limited.
  • the monomers may be mixed to initiate polymerization.
  • the monomers may be added sequentially to the polymerization system.
  • the heat-dissipating grease of this embodiment can be produced by kneading with a planetary stirrer, a universal mixer, a kneader, a hybrid mixer, or the like.
  • the copolymer was prepared by the following method. First, acrylic acid: 48.4 mol%, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate: 1.6 mol%, ⁇ -butyl- ⁇ -(3- 100 parts by mass of a (meth)acrylic monomer consisting of 50.0 mol % of methacryloxypropyl)polydimethylsiloxane (weight average molecular weight: 5,000) was added.
  • the polymerization rate for 100% of the charged amount of monomer was 98% or more when analyzed by gas chromatography analysis. From this, it was estimated that the ratio of each monomer unit in the copolymer was approximately the same as the charging ratio of the monomers.
  • the weight average molecular weight of the resulting copolymer was determined as the weight average molecular weight in terms of standard polystyrene using GPC (gel permeation chromatography).
  • GPC gel permeation chromatography
  • the measurement conditions are as follows. High-speed GPC device: "HLC-8020" manufactured by Tosoh Corporation Column: Tosoh Corporation "TSK guardcolumn MP (x L)" 6.0 mm ID ⁇ 4.0 cm 1 piece, and Tosoh Corporation "TSK-GELMULTIPOREHXL-M” 7.8 mm ID ⁇ 30.0 cm (theoretical plate number 16,000 plates ) 2, 3 in total (32,000 theoretical plates in total) Developing solvent: Tetrahydrofuran Detector: RI (differential refractometer)
  • composition of the monomers shown in Table 1 is expressed in molar ratio (%).
  • the molar ratio was calculated from the added amount and molecular weight of each monomer. Also, the molar ratio of ⁇ -butyl- ⁇ -(3-methacryloxypropyl)polydimethylsiloxane was calculated based on the weight average molecular weight.
  • composition and weight average molecular weight of the copolymer synthesized as described above are shown in Table 1 below.
  • the average particle size of the thermally conductive filler was measured using a "laser diffraction particle size distribution analyzer SALD-20" manufactured by Shimadzu Corporation.
  • An evaluation sample was obtained by adding 50 ml of pure water and 5 g of a thermally conductive filler to be measured to a glass beaker, stirring with a spatula, and then performing dispersion treatment with an ultrasonic cleaner for 10 minutes.
  • the dispersed liquid of the thermally conductive filler that had undergone the dispersion treatment was added drop by drop to the sampler section of the apparatus using a dropper, and measurement was performed when the absorbance was stabilized. D50 (median diameter) was adopted as the average particle size.
  • Thermal grease 1 The massive boron nitride particles, the silicone oil and the copolymer were weighed so that the proportion of the massive boron nitride particles was 30% by volume, the proportion of the silicone oil was 63% by volume, and the proportion of the copolymer was 7% by volume. was added to the universal blender. Then, the mixture was vacuum-heated and kneaded in a universal mixer at 150° C. for 3 hours under conditions of an absolute pressure of 100 Pa or less to prepare a heat-dissipating grease 1 . Table 2 shows the evaluation of the heat-dissipating grease 1 thus obtained.
  • Thermally conductive greases 2 to 14 were prepared in the same manner as thermally conductive grease 1 except that the components having the compositions shown in Tables 2 and 3 were used. described in
  • Thermo Scientific's rotary rheometer MARS III uses a 35 mm ⁇ parallel plate as the upper jig, and heat dissipation grease is placed on the 35 mm ⁇ lower plate whose temperature can be controlled with a Peltier element, and the thickness is 1 mm with the upper jig. and the protruding portion was scraped off, and the measurement was performed at 25°C.
  • the viscosity at a shear rate of 1 to 10 s -1 was measured, and the viscosity at a shear rate of 1 s -1 was used for evaluation.
  • the thermal conductivity of the thermal grease was measured according to ASTM D5470.
  • a rotational rheometer (“MARS III” manufactured by Thermo Scientific) was used to measure the minimum film thickness of the thermal grease. Specifically, a parallel plate of 8 mm ⁇ was used as an upper jig, thermal grease was placed on a lower plate of 35 mm ⁇ , and the thermal grease was compressed to a thickness of 1 mm by the upper jig. The thermal grease was further compressed for 10 minutes under the conditions of a load of 10 N and a shear rate of 1 s ⁇ 1 , and then the gap between the upper jig and the lower plate was measured, and the gap was taken as the minimum film thickness.
  • MERS III rotational rheometer
  • volume resistivity The volume resistivity of the thermal grease was measured according to JIS C2101.
  • the thermally conductive greases containing boron nitride particles and having a viscosity of 3000 Pa s or less when measured at 25° C. and at a shear rate of 1 s ⁇ 1 have a low specific gravity and a low viscosity. It was found to be a thermal grease with low and high thermal conductivity. Moreover, even a thermal grease having a viscosity of 3000 Pa s or less when measured at 25° C. and a shear rate of 1 s ⁇ 1 does not contain boron nitride particles. It has been found that a thermally conductive grease with high conductivity cannot be obtained.

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Abstract

Une graisse de dissipation de chaleur selon la présente invention comprend des particules de nitrure de bore, la viscosité mesurée à 25 °C et à un taux de cisaillement 1s-1 étant de 3 000 Pa·s ou moins. Grâce à la présente invention, il est possible de fournir une graisse de dissipation de chaleur ayant une faible densité spécifique et une faible viscosité.
PCT/JP2022/041845 2021-11-17 2022-11-10 Graisse de dissipation de chaleur WO2023090240A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000114438A (ja) * 1998-09-30 2000-04-21 Shin Etsu Chem Co Ltd 半導体装置
JP2003027080A (ja) * 2001-07-11 2003-01-29 Hitachi Ltd 熱伝導性グリース、その実装方法、電子部品の冷却方法、電子装置及び情報処理装置
JP2006257392A (ja) * 2005-03-14 2006-09-28 General Electric Co <Ge> 改良窒化ホウ素組成物及び該組成物を配合したポリマー系組成物
JP2008510878A (ja) * 2004-08-23 2008-04-10 ゼネラル・エレクトリック・カンパニイ 熱伝導性組成物およびその作製方法
US20140240928A1 (en) * 2011-10-07 2014-08-28 3M Innoovative Properties Company Thermal grease having low thermal resistance
JP2016162929A (ja) * 2015-03-03 2016-09-05 株式会社デンソー 放熱グリス、及びこれを用いた半導体冷却構造

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000114438A (ja) * 1998-09-30 2000-04-21 Shin Etsu Chem Co Ltd 半導体装置
JP2003027080A (ja) * 2001-07-11 2003-01-29 Hitachi Ltd 熱伝導性グリース、その実装方法、電子部品の冷却方法、電子装置及び情報処理装置
JP2008510878A (ja) * 2004-08-23 2008-04-10 ゼネラル・エレクトリック・カンパニイ 熱伝導性組成物およびその作製方法
JP2006257392A (ja) * 2005-03-14 2006-09-28 General Electric Co <Ge> 改良窒化ホウ素組成物及び該組成物を配合したポリマー系組成物
US20140240928A1 (en) * 2011-10-07 2014-08-28 3M Innoovative Properties Company Thermal grease having low thermal resistance
JP2016162929A (ja) * 2015-03-03 2016-09-05 株式会社デンソー 放熱グリス、及びこれを用いた半導体冷却構造

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