WO2024042956A1 - Graisse de dissipation de chaleur - Google Patents

Graisse de dissipation de chaleur Download PDF

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Publication number
WO2024042956A1
WO2024042956A1 PCT/JP2023/026975 JP2023026975W WO2024042956A1 WO 2024042956 A1 WO2024042956 A1 WO 2024042956A1 JP 2023026975 W JP2023026975 W JP 2023026975W WO 2024042956 A1 WO2024042956 A1 WO 2024042956A1
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filler
mass
silicone
content
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PCT/JP2023/026975
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Japanese (ja)
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和幸 五十嵐
貴之 岩崎
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デンカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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

Definitions

  • the present invention relates to thermal grease.
  • Metal heat sinks and casings are used for cooling, and thermally conductive materials are used to efficiently transfer heat from heat-generating electronic components to cooling parts such as heat sinks and casings.
  • thermally conductive materials are used to efficiently transfer heat from heat-generating electronic components to cooling parts such as heat sinks and casings.
  • Thermal conductive materials include thermosetting resin filled with thermally conductive filler, thermally conductive pads and sheets formed into sheets, and fluid resins filled with thermally conductive filler. There are heat-radiating greases that can be coated or made into thin films, and phase-change thermally conductive materials that soften or fluidize at the operating temperature of heat-generating electronic components.
  • Sheet-shaped heat dissipating materials are easy to handle and have excellent long-term shape retention, but they have high contact thermal resistance and are inferior to grease-like materials in terms of automatic mounting. Therefore, in recent years, heat dissipating grease has been increasingly used in thicknesses for which sheets were mainly used.
  • Such heat dissipating grease generally contains an inorganic filler in the resin that has been surface-treated with a silane coupling agent or the like.
  • a surface treatment agent other than a silane coupling agent for example, a copolymer containing a polybutadiene structural unit, a structural unit having a hydrolyzable silyl group, and a structural unit having a polysiloxane skeleton is known (for example, see Patent Document 1).
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a thermally conductive grease that is less prone to dripping while achieving low viscosity and high thermal conductivity.
  • the present invention is as follows.
  • [1] Contains a matrix component and a filler component,
  • the matrix component includes silicone A and surfactant B
  • the filler component includes filler D1 having a thermal conductivity of 20 W/m ⁇ k or more and silica D2,
  • the content of the silica D2 is 0.1 to 10% by mass with respect to the total amount of the filler components, Thermal grease.
  • the content of the filler component is 60 to 95% by volume based on the total amount of the thermal grease.
  • [3] The average particle size of the silica D2 is 20 ⁇ m or less, The heat dissipation grease described in [1] or [2].
  • the filler D1 further includes a filler D11 having an average particle size of 30 ⁇ m or more, The thermal grease according to any one of [1] to [3].
  • the silicone A is low molecular weight silicone A1 having a weight average molecular weight of 500 or more and 100,000 or less; Polymer silicone A2 having a weight average molecular weight of 150,000 or more and 1,000,000 or less, The heat dissipation grease according to any one of [1] to [4].
  • the content of the low molecular weight silicone A1 is 50 to 80% by mass based on the total amount of the matrix components, The heat dissipation grease described in [5].
  • the content of the polymeric silicone A2 is 3.0 to 25% by mass with respect to the total amount of the matrix components, The heat dissipation grease described in [5] or [6].
  • the content of the surfactant B is 5.0 to 45% by mass based on the total amount of the matrix components, The thermal grease according to any one of [1] to [7].
  • the matrix component further includes a silane coupling agent C.
  • the content of the silane coupling agent C is 2.0 to 10.0% by mass with respect to the total amount of the matrix components, The heat dissipation grease described in [9].
  • thermoly conductive grease that does not easily drip while achieving low viscosity and high thermal conductivity.
  • the present embodiment an embodiment of the present invention (hereinafter referred to as “the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. It is.
  • Thermal Grease contains a matrix component and a filler component, where the matrix component includes silicone A and surfactant B, and the filler component has a thermal conductivity of 20 W/m ⁇ k or more. filler D1 and silica D2, and the content of silica D2 is 0.1 to 10% by mass based on the total amount of the filler components.
  • Matrix component includes silicone A and surfactant B, and may further include silane coupling agent C and the like, if necessary.
  • silicone A The shape of silicone A is not particularly limited, but examples include non-crosslinked silicones such as linear silicones, branched silicones, and cyclic silicones; crosslinked silicones that are three-dimensionally crosslinked within the molecule. Among these, non-crosslinked silicones are preferred, and linear silicones are more preferred. By using such silicone A, the viscosity decreases and dripping tends to be further suppressed.
  • silicones contain monofunctional units (R 1 SiO 1/2 ), difunctional units (R 2 SiO 2/2 ), trifunctional units (R 3 SiO 3/2 ), and tetrafunctional units (SiO 4/2 ) .
  • linear silicone can be expressed as having a monofunctional unit (R 1 SiO 1/2 ) constituting the terminal and a bifunctional unit (R 2 SiO 2/2 ) constituting the main chain (see below)
  • n3, n4 0
  • branched silicones and three-dimensionally crosslinked silicones have trifunctional units (R 3 SiO 3/2 ) and/or tetrafunctional units (SiO 4/2 ) constituting branch points, and further have branched chains. It can be expressed as having a monofunctional unit (R 1 SiO 1/2 ) forming a terminal and a bifunctional unit (R 2 SiO 2/2 ) forming a branched chain.
  • n1 to n4 indicate the composition ratio of each unit, and can be expressed as a ratio such that the sum of n1 to n4 is 1. Note that whether or not these units are contained can be determined by a known method such as Si-NMR. Note that R 1 to R 4 can each independently represent any group. (R 1 SiO 1/2 ) n1 (R 2 SiO 2/2 ) n2 (R 3 SiO 3/2 ) n3 (SiO 4/2 ) n4
  • Silicone A is not particularly limited, but includes, for example, non-curing silicone and curable silicone.
  • the non-curing silicone resin is not particularly limited as long as it does not have a functional group that contributes to curing that the curable silicone resin has, or it is not used in combination with a catalyst.
  • the curable silicone is not particularly limited, but examples thereof include those using a combination of two types of silicones having functional groups that react with each other.
  • Such curable silicones include, but are not particularly limited to, addition-curing silicones, condensation-curing silicones, and peroxide-curing silicones.
  • silicone A is preferably a non-curing silicone.
  • silicone A it is possible to obtain a one-component heat dissipating grease, which tends to be easier to handle.
  • silicone A is not particularly limited, and examples thereof include dimethyl silicone, diphenyl silicone, and methylphenyl silicone. Further, these silicones may have an organic group introduced into their side chains and/or terminals. Examples of such silicones include, but are not limited to, non-reactive silicones such as long-chain alkyl-modified silicones, polyether-modified silicones, aralkyl-modified silicones, fatty acid ester-modified silicones, and fatty acid amide-modified silicones; amine-modified silicones, and epoxy Examples include reactive silicones such as modified silicones, mercapto-modified silicones, carboxyl-modified silicones, carbinol-modified silicones, and hydrogen-modified silicones.
  • non-reactive silicones such as long-chain alkyl-modified silicones, polyether-modified silicones, aralkyl-modified silicones, fatty acid ester-modified silicones, and fatty acid amide-modified silicones
  • dimethyl silicone diphenyl silicone, methylphenyl silicone, and non-reactive silicone are preferred, and dimethyl silicone is more preferred.
  • the content of silicone A may be preferably 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more based on the total amount of matrix components. % or more. Further, the content of silicone A may preferably be 90% by mass or less, 85% by mass or less, or 80% by mass or less with respect to the total amount of the matrix components. When the content of silicone A with respect to the total amount of matrix components is within the above range, the viscosity tends to decrease and dripping is further suppressed.
  • Silicone A may contain at least one of a low-molecular silicone A1 having a weight average molecular weight of 500 or more and 100,000 or less and a high-molecular silicone A2 having a weight average molecular weight of 150,000 or more and 1,000,000 or less, or may contain both. Among these, it is preferable to include both low-molecular-weight silicone A1 and high-molecular-weight silicone A2. By using low-molecular-weight silicone A1 and high-molecular-weight silicone A2, the viscosity tends to decrease and dripping is further suppressed.
  • the weight average molecular weight of the low molecular weight silicone A1 is 500 or more, preferably 1000 or more, 1500 or more, 2000 or more, or 2500 or more.
  • the weight average molecular weight of the low molecular weight silicone A1 is 100,000 or less, preferably 50,000 or less, 25,000 or less, 15,000 or less, or 10,000 or less. In most cases, it may be 7500 or less.
  • the viscosity of the low-molecular silicone A1 at 25° C. may preferably be 1.0 mPa ⁇ s or more, 5.0 mPa ⁇ s or more, 10 mPa ⁇ s or more, or 20 mPa ⁇ s. s or more, or 30 mPa ⁇ s or more. Further, the viscosity of the low molecular weight silicone A1 at 25° C. may preferably be 5000 mPa ⁇ s or less, 4000 mPa ⁇ s or less, 3000 mPa ⁇ s or less, or 2000 mPa ⁇ s or less. It may be 1000 mPa ⁇ s or less. When the viscosity of the low-molecular silicone A1 is within the above range, the viscosity decreases and dripping tends to be further suppressed.
  • the content of low molecular weight silicone A1 may be preferably 50% by mass or more, 55% by mass or more, or 60% by mass or more, based on the total amount of the matrix components. It may be 65% by mass or more. When the content of low molecular weight silicone A1 is 50% by mass or more based on the total amount of matrix components, the viscosity tends to decrease.
  • the content of low molecular weight silicone A1 may be preferably 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of the matrix components. It may be 65% by mass or less. When the content of low molecular weight silicone A1 is 80% by mass or less with respect to the total amount of matrix components, dripping tends to be further suppressed.
  • the weight average molecular weight of the polymer silicone A2 may be 150,000 or more, preferably 200,000 or more, 250,000 or more, 300,000 or more, 350,000 or more. Good too.
  • the weight average molecular weight of the polymeric silicone A2 may be 1,000,000 or less, preferably 900,000 or less, 800,000 or less, 700,000 or less, and 600,000 or less. There may be. By using such polymeric silicone A2, the viscosity tends to decrease and dripping is further suppressed.
  • the viscosity of the polymeric silicone A2 at 25° C. may preferably be 1000 Pa ⁇ s or more, 2500 Pa ⁇ s or more, 5000 Pa ⁇ s or more, or 7500 Pa ⁇ s or more.
  • the pressure may be 10,000 Pa ⁇ s or more.
  • the viscosity of the polymer silicone A2 at 25° C. may preferably be 50,000 mPa ⁇ s or less, 40,000 mPa ⁇ s or less, 30,000 mPa ⁇ s or less, or 20,000 mPa ⁇ s or less. It may be 15000 mPa ⁇ s or less.
  • the content of polymeric silicone A2 is preferably 3.0% by mass or more, 5.0% by mass or more, 7.0% by mass or more based on the total amount of matrix components. It may be 9.0% by mass or more, or it may be 12% by mass or more. When the content of polymer silicone A2 is 3.0% by mass or more with respect to the total amount of matrix components, dripping tends to be further suppressed.
  • the content of polymeric silicone A2 may be preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less, based on the total amount of the matrix components. It may be 12.5% by mass or less. When the content of polymer silicone A2 is 25% by mass or less with respect to the total amount of matrix components, the viscosity tends to decrease.
  • the ratio of the content of low molecular weight silicone A1 to the content of high molecular weight silicone A2 may preferably be 1.5 or more, 2.0 or more, and 2.5 or more, may be 3.0 or more, may be 3.5 or more, or may be 4.0 or more. Further, the ratio of the content of low molecular weight silicone A1 to the content of high molecular weight silicone A2 (A1/A2) may be preferably 10 or less, 9.0 or less, and 8.0 It may be below, 7.0 or less, or 6.0 or less. When the ratio (A1/A2) is within the above range, the viscosity decreases and dripping tends to be further suppressed.
  • Surfactant B is not particularly limited. Among these, as surfactant B, a polymer having a silicone (meth)acrylic monomer unit ⁇ is preferable, and a polymer having a (meth)acrylic monomer unit ⁇ having an anionic group and a cationic group is preferable. A copolymer having a (meth)acrylic monomer unit ⁇ and a silicone (meth)acrylic monomer unit ⁇ is more preferable.
  • surfactant B By using such surfactant B, the dispersibility of the filler component can be maintained. Therefore, even if the filler component is highly loaded from the viewpoint of thermal conductivity, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of surfactant B may be preferably 5.0% by weight or more, 10% by weight or more, or 15% by weight or more based on the total amount of matrix components.
  • the amount may be 20% by weight or more.
  • the content of surfactant B may be preferably 45% by weight or less, 40% by weight or less, or 35% by weight or less based on the total amount of matrix components. It may be 30% by weight or less, or 20% by weight or less.
  • the content of surfactant B may be preferably 5.0 parts by weight or more, 10 parts by weight or more, and 15 parts by weight relative to 100 parts by weight of silicone A.
  • the amount may be 20 parts by weight or more, or 25 parts by weight or more.
  • the content of surfactant B may be preferably 45 parts by weight or less, 40 parts by weight or less, and 35 parts by weight or less with respect to 100 parts by weight of silicone A.
  • the amount may be 30 parts by weight or less.
  • (meth)acrylic includes acrylic and methacryl
  • (meth)acrylic monomer includes (meth)acrylate and (meth)acrylamide.
  • (meth)acrylic monomer unit ⁇ etc. are also simply referred to as “unit ⁇ ” etc.
  • the (meth)acrylic monomer unit ⁇ is a repeating unit having an anionic group.
  • the anionic group include, but are not limited to, a carboxy group, a phosphoric acid group, a phenolic hydroxy group, and a sulfonic acid group.
  • the anionic group include, but are not limited to, a carboxy group, a phosphoric acid group, a phenolic hydroxy group, and a sulfonic acid group.
  • one or more types selected from the group consisting of a carboxy group, a phosphoric acid group, and a phenolic hydroxy group are preferable. Having such a group tends to further improve the dispersibility of the filler component.
  • the unit ⁇ 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 filler component.
  • the unit ⁇ has no electron-donating group bonded to the anionic group or has a group with low electron-donating property.
  • 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 a substituent of an electron-donating group such as a methyl group on the carbon atom at the ⁇ -position of the carboxy group may be used. With such a structure, the dispersibility of the filler component tends to be further improved.
  • Such (meth)acrylic monomers are not particularly limited, but include, for example, acrylic acid, methacrylic acid, acid phosphoxypropyl methacrylate, acid phosphoxy polyoxyethylene glycol monomethacrylate, acid phosphoxy poly 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- Examples include acrylamide-2-methylpropanesulfonic acid.
  • acrylic acid 2-methacryloyloxyethyl acid phosphate, 4-hydroxyphenyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid are preferred, and acrylic acid is more preferred.
  • acrylic acid is more preferred.
  • the unit ⁇ may be used alone or in combination of two or more types.
  • the content of the unit ⁇ may be preferably 1.0 mol% or more and 5.0 mol% or less with respect to the total 100 mol% of the unit ⁇ , unit ⁇ , and unit ⁇ . Often, it may be 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, or 45 mol% or more. good. Further, the content of the unit ⁇ may be preferably 85 mol% or less, or 80 mol% or less, with respect to the total 100 mol% of the unit ⁇ , unit ⁇ , and unit ⁇ , It may be 75 mol% or less, or 70 mol% or less. When the content of the unit ⁇ is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the molar ratio of the unit ⁇ to the unit ⁇ may preferably be 0.5 or more, 1.0 or more, 2.5 or more, and 5.0 or more. It may be 10 or more, 15 or more, 20 or more, or 25 or more. Further, the molar ratio of the unit ⁇ to the unit ⁇ may preferably be 150 or less, 100 or less, 75 or less, 50 or less, and 40 or less. There may be. When the molar ratio of the units ⁇ to the units ⁇ is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the (meth)acrylic monomer unit ⁇ is a repeating unit having a cationic group.
  • the cationic group is not particularly limited, but is preferably one or more selected from the group consisting of, for example, a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium salt. .
  • tertiary amino groups are more preferred. Having such a group tends to further improve the dispersibility of the filler component.
  • the unit ⁇ 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 filler component.
  • the unit ⁇ has no electron-withdrawing group bonded to the cationic group or has a group with low electron-withdrawing property.
  • 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 a substituent of an electron-withdrawing group such as a carboxyl group on the ⁇ -position carbon atom of the amino group may be used. With such a structure, the dispersibility of the filler component tends to be further improved.
  • Such (meth)acrylic monomers are not particularly limited, but include, for example, 1-aminoethyl acrylate, 1-aminopropyl acrylate, 1-aminoethyl methacrylate, 1-aminopropyl methacrylate, dimethylaminoethyl methacrylate, Diethylaminoethyl methacrylate, t-butylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylate quaternary salt, acrylic acid-1,2,2,6,6-pentamethyl-4-piperidyl, methacrylic acid-1,2,2, Examples include 6,6-pentamethyl-4-piperidyl, 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 acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 1-aminoethyl methacrylate are preferred; More preferred are 1,2,2,6,6-pentamethyl-4-piperidyl acid and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate.
  • the units ⁇ may be used alone or in combination of two or more.
  • the content of the unit ⁇ is preferably 0.05 mol% or more, or even 0.10 mol% or more with respect to the total 100 mol% of the unit ⁇ , unit ⁇ , and unit ⁇ .
  • the content may be 0.50 mol% or more, 1.00 mol% or more, or 1.50 mol% or more.
  • the content of the unit ⁇ may be preferably 10 mol% or less, or even 8.0 mol% or less, with respect to the total 100 mol% of the unit ⁇ , unit ⁇ , and unit ⁇ . Generally, it may be 10 mol% or less, 6.0 mol% or less, 2.0 mol% or less, or 3.0 mol% or less.
  • the (meth)acrylic monomer unit ⁇ is a silicone (meth)acrylic monomer unit, and is a (meth)acrylic monomer that does not contain a cationic group or anionic group in its molecule and has a silicone group. It is the body.
  • the (meth)acrylic monomer ⁇ preferably has a skeleton that has high affinity or compatibility with other matrix components.
  • the (meth)acrylic monomer ⁇ has a silicone skeleton such as dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc. as such a skeleton.
  • Such (meth)acrylic monomers are not particularly limited, but include, for example, (meth)acrylic monomers having a siloxane skeleton such as ⁇ -butyl- ⁇ -(3-methacryloxypropyl) polydimethylsiloxane. Examples include the body.
  • the unit ⁇ may be used alone or in combination of two or more types.
  • the weight average molecular weight of the (meth)acrylic monomer ⁇ may be preferably 300 or more, 1000 or more, 2000 or more, or 3000 or more, It may be 4000 or more. Further, the weight average molecular weight of the (meth)acrylic monomer ⁇ may preferably be 20,000 or less, 17,500 or less, 15,000 or less, or 12,500 or less. It may be 10,000 or less, or 7,500 or less. Furthermore, when the weight average molecular weight of the (meth)acrylic monomer ⁇ is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of the unit ⁇ is preferably 10 mol % or more, 15 mol % or more, and 20 mol % with respect to the total 100 mol % of the unit ⁇ , unit ⁇ , and unit ⁇ . % or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, or 40 mol% or more. Further, the content of the unit ⁇ may be preferably 90 mol% or less, or 80 mol% or less, with respect to the total 100 mol% of the unit ⁇ , unit ⁇ , and unit ⁇ , It may be 70 mol% or less, 60 mol% or less, or 50 mol% or less. When the content of the unit ⁇ is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the weight average molecular weight of surfactant B may be preferably 5,000 or more, 7,500 or more, 10,000 or more, 20,000 or more, 30,000 or more. It may be 40,000 or more, or it may be 50,000 or more.
  • the weight average molecular weight of the surfactant B is 5,000 or more, the dispersibility can be maintained even when the temperature is maintained at high temperature for a long time, and an increase in the hardness of the thermal grease can be suppressed. In addition to this, dripping tends to be further suppressed.
  • the weight average molecular weight of surfactant B may preferably be 500,000 or less, 250,000 or less, 150,000 or less, 125,000 or less, and 100,000 or less. It may be 75,000 or less. When the weight average molecular weight of surfactant B is 500,000 or less, the viscosity of the heat dissipating grease tends to be further reduced and the handleability is further improved.
  • each weight average molecular weight can be determined by GPC (gel permeation chromatography).
  • the viscosity of surfactant B at 25°C is preferably 10 mPa ⁇ s or more, 50 mPa ⁇ s or more, 75 mPa ⁇ s or more, 100 mPa ⁇ s or more. There may be. Further, the viscosity of surfactant B at 25° C. may preferably be 2000 mPa ⁇ s or less, 1500 mPa ⁇ s or less, 1000 mPa ⁇ s or less, and 750 mPa ⁇ s or less. It may be. When the viscosity of surfactant B is within the above range, changes in hardness and dripping tend to be further suppressed.
  • the method for producing surfactant B is not particularly limited, and known polymerization methods for (meth)acrylic monomers can be used. Examples of polymerization methods include radical polymerization and anionic polymerization. Among these, radical polymerization is preferred.
  • Thermal polymerization initiators used in radical polymerization are not particularly limited, but include, for example, azo compounds such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, and di-tert-butyl peroxide. Examples include things.
  • the photopolymerization initiator used in radical polymerization is not particularly limited, but includes benzoin derivatives.
  • known polymerization initiators used in living radical polymerization such as ATRP and RAFT can also be used.
  • the polymerization conditions are not particularly limited and can be adjusted as appropriate depending on the boiling point of the initiator and solvent used, and the type of monomer.
  • the order of adding the monomers is not particularly limited, but for example, from the viewpoint of synthesizing a random copolymer, the monomers may be mixed to start polymerization, or from the viewpoint of synthesizing a block copolymer, the monomers may be added to start polymerization.
  • the polymers may be added sequentially to the polymerization system.
  • Silane coupling agent C The matrix component may further include a silane coupling agent C.
  • a silane coupling agent C By including the silane coupling agent C, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • silane coupling agent C examples include, but are not limited to, epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminopropyltriethoxysilane; Examples include aminosilanes such as ureidopropyltriethoxysilane and N-phenylaminopropyltrimethoxysilane; hydrophobic silane compounds such as phenyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, and n-decyltrimethoxysilane.
  • epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane
  • hydrophobic silane compounds are more preferred.
  • silane coupling agent C By using such a silane coupling agent C, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of the silane coupling agent C may be preferably 2.0% by mass or more, 4.0% by mass or more, and 6.0% by mass with respect to the total amount of matrix components. It may be more than 8.0% by mass. Further, the content of the silane coupling agent C may be preferably 10.0% by mass or less, 8.0% by mass or less, and 6.0% by mass or less, based on the total amount of the matrix components. It may be less than 4.0% by mass, or less than 4.0% by mass. When the content of the silane coupling agent C is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the filler component includes filler D1 having a thermal conductivity of 20 W/m ⁇ k or more and silica D2, and optionally, filler D1 having a thermal conductivity of 20 W/m ⁇ k or more and other materials other than silica D2.
  • the filler D3 may further be included.
  • the content of the filler component may be preferably 60% by volume or more, 65% by volume or more, 70% by volume or more, 75% by volume or more, based on the total amount of the thermal grease. % or more, and may be 80 volume % or more. Further, the content of the filler component may be preferably 95% by volume or less, 90% by volume or less, or 85% by volume or less, based on the total amount of the thermal grease. It may be 80% by volume or less. When the content of the filler component is within the above range, thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • Each filler component may be surface-treated with a surface treatment agent by a known wet treatment method or dry treatment method.
  • a surface treatment agent is not particularly limited, for example, the above-mentioned silane coupling agent C may be mentioned, but the silane coupling agent C may be added separately regardless of this surface treatment.
  • the thermal conductivity of the filler D1 may be 20 W/m ⁇ k or more.
  • the upper limit of the thermal conductivity of the filler D1 is not particularly limited, but may be, for example, 350 W/m ⁇ k or less. By using such filler D1, thermal conductivity tends to be further improved.
  • Such filler D1 is not particularly limited, but includes, for example, aluminum oxide (hereinafter also referred to as "alumina”), aluminum nitride, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metallic aluminum, magnesium oxide, and diamond. , carbon, indium, gallium, copper, silver, iron, nickel, gold, tin, metallic silicon, and the like.
  • alumina aluminum oxide
  • aluminum nitride aluminum nitride
  • boron nitride silicon nitride
  • zinc oxide aluminum hydroxide
  • metallic aluminum magnesium oxide
  • diamond diamond
  • carbon indium, gallium, copper, silver, iron, nickel, gold, tin, metallic silicon, and the like.
  • filler D1 it is preferable to contain at least one selected from the group consisting of aluminum oxide, aluminum nitride, boron nitride, silicon nitride, zinc oxide, aluminum hydroxide, metal aluminum, magnesium oxide, copper, silver, and diamond; is more preferable.
  • the content of filler D1 may be preferably 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more based on the total amount of the heat dissipation filler. % or more, and may be 80% by mass or more. Further, the content of filler D1 may be preferably 97% by mass or less, 95% by mass or less, or 93% by mass or less, based on the total amount of the heat dissipation filler. It may be 87% by mass or less. When the content of filler D1 is within the above range, thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of filler D1 may be preferably 90% by mass or more, 92% by mass or more, or 94% by mass or more, based on the total amount of filler components. It may be 96% by mass or more, or 98% by mass or more. Further, the content of filler D1 may be preferably 99.9% by mass or less, 99.7% by mass or less, and 99.5% by mass or less based on the total amount of filler components. The content may be 99.3% by mass or less, or may be 99.0% by mass or less.
  • the average particle size of filler D1 is preferably 0.1 to 120 ⁇ m, more preferably 0.1 to 60 ⁇ m. When the average particle size of the filler D1 is within the above range, fluidity, dispersibility, and filling properties tend to be further improved. Note that the average particle diameter in this embodiment means D50 (median diameter).
  • the filler D1 may be a mixture of fillers having different average particle diameters.
  • filler D1 can be any of filler D11 with an average particle size of 30 ⁇ m or more, filler D12 with an average particle size of 1.0 ⁇ m or more and less than 30 ⁇ m, and filler D13 with an average particle size of 0.10 ⁇ m or more and less than 1.0 ⁇ m. or may be used in combination.
  • thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the filler D1 further includes a filler D11 having an average particle size of 30 ⁇ m or more. This tends to further improve thermal conductivity.
  • the average particle diameter of filler D11 may be 30 ⁇ m or more, preferably 35 ⁇ m or more, or 40 ⁇ m or more. Further, the average particle size of filler D11 may preferably be 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 60 ⁇ m or less. Good too. When the average particle size of the filler D11 is within the above range, the thermal conductivity is further improved, the viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of filler D11 may be preferably 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, based on the total amount of filler D1. % or more. Further, the content of filler D11 may be preferably 75% by mass or less, 70% by mass or less, or 65% by mass or less, based on the total amount of filler D1. It may be 60% by mass or less.
  • thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the average particle size of filler D12 may be 1.0 ⁇ m or more, preferably 1.5 ⁇ m or more, 2.0 ⁇ m or more, or 2.5 ⁇ m or more. . Further, the average particle size of the filler D12 is less than 30 ⁇ m, preferably 25 ⁇ m or less, 20 ⁇ m or less, or 15 ⁇ m or less. When the average particle size of filler D12 is within the above range, thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of filler D12 may be preferably 5.0% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total amount of filler D1. It may be 20% by mass or more.
  • the content of filler D12 may be preferably 40% by mass or more, 35% by mass or more, 30% by mass or more, 25% by mass or more, based on the total amount of filler D1. % or more.
  • the average particle size of filler D13 may be 0.10 ⁇ m or more, preferably 0.20 ⁇ m or more, or 0.30 ⁇ m or more. Further, the average particle size of filler D13 is less than 1.0 ⁇ m, preferably 0.80 ⁇ m or less, 0.60 ⁇ m or less, or 0.50 ⁇ m or less. When the average particle size of filler D13 is within the above range, thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of filler D13 may be preferably 5.0% by mass or more, 7.5% by mass or more, or 10% by mass or more based on the total amount of filler D1. It may be 12.5% by mass or more.
  • the content of filler D13 may be preferably 25% by mass or more, 22.5% by mass or more, or 20% by mass or more with respect to the total amount of filler D1, It may be 17.5% by mass or more.
  • the average particle size of silica D2 may preferably be 20 ⁇ m or less, 16 ⁇ m or less, 12 ⁇ m or less, 8.0 ⁇ m or less, and 4.0 ⁇ m or less. There may be. Further, the average particle size of silica D2 may preferably be 0.10 ⁇ m or more, 0.10 ⁇ m or more, 0.30 ⁇ m or more, or 0.50 ⁇ m or more. The thickness may be 1.0 ⁇ m or more, or 2.0 ⁇ m or more. When the average particle size of silica D2 is within the above range, the viscosity tends to be further reduced and changes in hardness are further suppressed. In addition to this, dripping tends to be further suppressed.
  • the content of silica D2 may be 0.1% by mass or more, preferably 0.3% by mass or more, and 0.5% by mass or more based on the total amount of filler components. It may be 0.7% by mass or more, or it may be 1.0% by mass or more. Further, the content of silica D2 may be 10% by mass or less, preferably 8.0% by mass or less, and 6.0% by mass or more with respect to the total amount of filler components. The content may be 4.0% by mass or less, or may be 2.0% by mass or less. When the content of silica D2 is within the above range, thermal conductivity is further improved, viscosity is further reduced, and changes in hardness tend to be further suppressed. In addition to this, dripping tends to be further suppressed.
  • the electronic device of this embodiment includes a heat generating element, a heat sink, and the above-mentioned heat-radiating grease, and the heat-radiating grease is disposed between the heat generating element and the heat sink.
  • the heating element and the heat sink are thermally coupled via thermal grease.
  • examples of the heating element include, but are not particularly limited to, electronic components that generate heat such as a motor, a battery pack, a circuit board used in an on-vehicle power supply system, a power transistor, and a microprocessor.
  • electronic components used in on-vehicle power supply systems are preferred.
  • the heat sink is not particularly limited as long as it is a component configured for the purpose of heat radiation or heat absorption.
  • an electronic device may be obtained by bonding a heat generating element and a heat sink using thermal grease.
  • thermal grease (Examples 1 to 6 and Comparative Examples 1 to 4) Silicone A, surfactant B, silane coupling agent C, and filler D were mixed to prepare a thermal grease having the composition shown in Table 1.
  • Table 1 the composition of each component is described so that the matrix component and the filler component each have a total of 100 parts by weight.
  • the mixing ratio of the matrix component and the filler component is expressed as the total filling amount of the filler component.
  • the following evaluations were performed using each of the obtained heat dissipation greases. The results are shown in Table 1.
  • the average particle diameter of each filler component was measured using a "laser diffraction particle size distribution analyzer SALD-20" manufactured by Shimadzu Corporation.
  • SALD-20 laser diffraction particle size distribution analyzer
  • 50 ml of pure water and 5 g of each filler component to be measured were added to a glass beaker, stirred using a spatula, and then dispersed in an ultrasonic cleaner for 10 minutes.
  • the dispersion liquid of each filler component subjected to the dispersion treatment was added drop by drop to the sampler part of the apparatus using a dropper, and measurement was performed when the absorbance became stable.
  • D50 median diameter
  • the polymerization rate based on 100% monomer charge amount was 98% or more when analyzed by gas chromatography. From this, it was estimated that the ratio of each monomer unit in surfactant B was approximately the same as the monomer loading ratio. That is, surfactant B was a copolymer containing 67.7 mol% of units ⁇ , 2.3 mol% of units ⁇ , and 30 mol% of units ⁇ .
  • the weight average molecular weight of the obtained surfactant B was determined as a standard polystyrene equivalent weight average molecular weight using GPC (gel permeation chromatography) method, and was found to be 85,000. Note that the measurement conditions are as follows.
  • High-speed GPC device “HLC-8020” manufactured by Tosoh Corporation Column: 1 piece of “TSK guardcolumn MP (xL)” 6.0 mm ID x 4.0 cm manufactured by Tosoh Corporation, and 2 "TSK-GELMULTIPOREHXL-M” 7.8 mm ID x 30.0 cm (number of theoretical plates 16,000) manufactured by Tosoh Corporation 3 books in total (total number of theoretical plates 32,000) Developing solvent: Tetrahydrofuran Detector: RI (differential refractometer)
  • Discharge A syringe filled with each heat dissipating grease was set in the dispensing machine, and a nozzle having a discharging opening with a diameter of 3 mm was installed at the tip of the syringe. Then, the discharge amount when the grease filled in the syringe was discharged under conditions of a predetermined discharge pressure of 0.5 MPa and a discharge time of 5 seconds was confirmed.
  • Table 1 shows the discharge amount measured immediately after adjusting the thermal grease, the discharge amount measured after storing the thermal grease for one month at room temperature, and the discharge amount measured after storing the thermal grease for three months at room temperature. Showing the results of quantity.
  • the aluminum plate 10 and the glass plate 13 were fixed with clips 14 and left standing vertically, and after performing 3000 cycles of -40°C for 30 minutes and 150°C for 30 minutes.
  • the dripping properties were evaluated by observing the deviation of the thermal grease from its initial position. (Evaluation criteria) A: The deviation of the thermal grease from the initial position is 0.5 mm or less B: The deviation of the thermal grease from the initial position is more than 0.5 mm and 2 mm or less C: The deviation of the thermal grease from the initial position exceeds 2 mm
  • the heat dissipation grease of the present invention has industrial applicability as a heat dissipation grease for thermally connecting a heat generating element and a heat sink in electronic equipment.

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Abstract

L'invention concerne une graisse de dissipation de chaleur qui comprend un composant de matrice et un composant de charge. Le composant de matrice comprend une silicone A et un tensioactif B, et le composant de charge comprend une charge D1 ayant une conductivité thermique d'au moins 20 W/m · k et une silice D2. La teneur en silice D2 est de 0,1 à 10 % en masse par rapport à la quantité totale du composant de charge.
PCT/JP2023/026975 2022-08-26 2023-07-24 Graisse de dissipation de chaleur WO2024042956A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016216523A (ja) * 2015-05-14 2016-12-22 デンカ株式会社 熱伝導性グリース用組成物、熱伝導性グリースおよび放熱部材
JP2020059842A (ja) * 2018-10-01 2020-04-16 トヨタ自動車株式会社 放熱グリース組成物及び電子機器
WO2020080256A1 (fr) * 2018-10-15 2020-04-23 デンカ株式会社 Ensemble de composition durcissable à deux composants, produit durci thermoconducteur, et dispositif électronique
WO2020209263A1 (fr) * 2019-04-11 2020-10-15 デンカ株式会社 Copolymère, dispersant et composition de résine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016216523A (ja) * 2015-05-14 2016-12-22 デンカ株式会社 熱伝導性グリース用組成物、熱伝導性グリースおよび放熱部材
JP2020059842A (ja) * 2018-10-01 2020-04-16 トヨタ自動車株式会社 放熱グリース組成物及び電子機器
WO2020080256A1 (fr) * 2018-10-15 2020-04-23 デンカ株式会社 Ensemble de composition durcissable à deux composants, produit durci thermoconducteur, et dispositif électronique
WO2020209263A1 (fr) * 2019-04-11 2020-10-15 デンカ株式会社 Copolymère, dispersant et composition de résine

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