WO2022044723A1 - Composition thermoconductrice et feuille thermoconductrice l'utilisant - Google Patents

Composition thermoconductrice et feuille thermoconductrice l'utilisant Download PDF

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WO2022044723A1
WO2022044723A1 PCT/JP2021/028782 JP2021028782W WO2022044723A1 WO 2022044723 A1 WO2022044723 A1 WO 2022044723A1 JP 2021028782 W JP2021028782 W JP 2021028782W WO 2022044723 A1 WO2022044723 A1 WO 2022044723A1
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heat conductive
heat
thermally conductive
conductive composition
conductive sheet
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Japanese (ja)
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昌幸 松島
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デクセリアルズ株式会社
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    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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

Definitions

  • This technology relates to a heat conductive composition and a heat conductive sheet using the same.
  • This application claims priority on the basis of Japanese Patent Application No. 2020-142900 filed on August 26, 2020 in Japan, and this application is referred to in this application. It will be used.
  • a material called a thermal interface material which relaxes the thermal resistance of the path through which heat generated from a semiconductor element is released to a heat sink, a housing, or the like, is in the form of a sheet, gel, or the like. It is used in various forms such as grease.
  • thermal interface material examples include a composite material (heat conductive composition) in which a heat conductive filler is dispersed in an epoxy resin or a silicone resin.
  • a heat conductive filler metal oxides and metal nitrides are often used.
  • silicone resin which is an example of resin, is widely used from the viewpoint of heat resistance and flexibility.
  • the flexibility of the obtained heat conductive sheet tends to decrease.
  • the stress applied to the semiconductor element having a relatively weak strength is large, and an unreasonable force is applied to the semiconductor element. become.
  • the stress applied to the substrate also increases, the stress on the substrate increases, and the substrate may bend. There is a concern that the semiconductor element mounted on the substrate may be peeled off due to such bending of the substrate.
  • the heat conductive sheet is usually sandwiched between the heat generating member and the heat radiating member by applying a load.
  • the heat generating member or the heat radiating member has a concave portion or a convex portion
  • the surface of the heat conductive sheet may not sufficiently contact the concave portion or the convex portion of the heat generating member or the heat radiating member.
  • a heat conductive sheet having poor followability (flexibility) to the contacting member is used, there is a concern that the heat conductivity of the heat conductive sheet may be lowered.
  • This technique has been proposed in view of such conventional circumstances, and is a heat conductive composition capable of forming a heat conductive sheet having good heat conductivity and flexibility, and a heat conductive sheet using the same.
  • the purpose is to provide.
  • a predetermined acrylic-silicone copolymer is contained in a heat conductive composition containing an organopolysiloxane, a heat conductive filler, and an alkoxysilane compound, and an alkoxy is obtained with respect to the organopolysiloxane. It has been found that the above-mentioned problems can be solved by setting the total content of the silane compound and the siloxane-modified acrylic resin to a predetermined value or more.
  • the thermally conductive composition according to the present technology contains an organopolysiloxane, a thermally conductive filler, an alkoxysilane compound, and a siloxane-modified acrylic resin, and the content of the organopolysiloxane is 100 parts by mass. , The total content of the alkoxysilane compound and the siloxane-modified acrylic resin is 100 parts by mass or more.
  • the heat conductive sheet according to the present technology is made of a cured product of the above heat conductive composition.
  • FIG. 1 is a cross-sectional view showing an example of a heat conductive sheet.
  • FIG. 2 is a cross-sectional view showing an example of a semiconductor device.
  • the thermally conductive composition according to the present technology contains an organopolysiloxane, a thermally conductive filler, an alkoxysilane compound, and a siloxane-modified acrylic resin. Further, in the heat conductive composition, when the content of organopolysiloxane is 100 parts by mass, the total content of the alkoxysilane compound and the siloxane-modified acrylic resin is 100 parts by mass or more, and 200 parts by mass or more. It may be 300 parts by mass or more, 400 parts by mass or more, 500 parts by mass or more, 600 parts by mass or more, or 700 parts by mass or more. It may be 800 parts by mass or more.
  • the upper limit of the total content of the alkoxysilane compound and the siloxane-modified acrylic resin is not particularly limited, and is, for example, 1000 parts by mass. It can be as follows. Hereinafter, each component will be described in detail.
  • the thermally conductive composition according to the present technology contains organopolysiloxane from the viewpoints of molding processability, weather resistance, adhesion to electronic components, followability, and the like.
  • Organopolysiloxane refers to a polymer compound in which an organic group is added to a structure having a portion in which a silicon atom is bonded to another silicon atom via oxygen.
  • Organopolysiloxane usually refers to an organic polymer having a siloxane bond as a main chain.
  • Organopolysiloxane can be cured by applying thermal energy, light energy, or the like in the presence of a curing catalyst.
  • the organopolysiloxane is classified according to the curing mechanism, and examples thereof include an addition polymerization curing type (addition reaction type), a polypolymerization curing type (condensation type), an ultraviolet curing type, and a peroxide fusing type.
  • the organopolysiloxane may be used alone or in combination of two or more.
  • organopoly is used from the viewpoint of adhesion between the heat generating surface and the heat sink surface of the electronic component.
  • an addition reaction type silicone resin (additional reaction type liquid silicone resin) as the siloxane.
  • the addition reaction type silicone resin include (i) a main agent containing silicone having an alkenyl group as a main component, (ii) a main agent containing a curing catalyst, and (iii) a curing agent having a hydrosilyl group (Si—H group).
  • the addition reaction type silicone resin include (i) a main agent containing silicone having an alkenyl group as a main component, (ii) a main agent containing a curing catalyst, and (iii) a curing agent having a hydrosilyl group (Si—H group). Examples thereof include a two-component addition reaction type silicone resin comprising.
  • the (ii) curing catalyst is a catalyst for promoting an addition reaction between (i) an alkenyl group in a silicone having an alkenyl group and (iii) a hydrosilyl group in a curing agent having a hydrosilyl group.
  • Examples of the curing catalyst include well-known catalysts as catalysts used in the hydrosilylation reaction, and for example, platinum group curing catalysts such as platinum group metals such as platinum, rhodium and palladium, platinum chloride and the like may be used. Can be done.
  • the curing agent having a hydrosilyl group for example, an organopolysiloxane having a hydrosilyl group can be used.
  • the organopolysiloxane component may contain a silicone resin containing a Si—OH group.
  • the silicone resin containing a Si—OH group is a group consisting of M unit (R 3 SiO 1/2 ), Q unit (SiO 2 ), T unit (RSiO 3/2 ) and D unit (R 2 SiO). Examples thereof include an organopolysiloxane composed of a copolymer having at least one unit (R represents a monovalent hydrocarbon group or a hydroxyl group) selected from the above.
  • an organopolysiloxane (MQ resin) made of a copolymer having M units and Q units is preferable.
  • the addition reaction type silicone resin which is an example of organopolysiloxane
  • a desired commercially available product can be used in consideration of the hardness of the cured product obtained by curing the heat conductive composition.
  • CY52-276, CY52-272, EG-3100, EG-4000, EG-4100, 527 above, manufactured by Toray Dow Corning
  • KE-1800T, KE-1031, KE-1051J aboveve, Shin-Etsu Chemical. (Made by Kogyo Co., Ltd.).
  • the heat conductive filler can be selected from known materials in view of the desired thermal conductivity and filling property, for example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, aluminum, copper and silver. Examples thereof include metals such as, alumina, metal oxides such as magnesium oxide, metal nitrides such as aluminum nitride, boron nitride and silicon nitride, carbon nanotubes, metallic silicon and fiber fillers (glass fiber, carbon fiber).
  • the heat conductive filler may be used alone or in combination of two or more.
  • the thermally conductive composition according to the present technology preferably contains, for example, an inorganic filler as a thermally conductive filler, more preferably a nitrogen compound, and heat, from the viewpoint of achieving good flame retardancy. It is more preferable to contain a nitrogen compound having a conductivity of 60 W / m ⁇ K or more. As such a nitrogen compound, aluminum nitride or boron nitride is preferable, and aluminum nitride is more preferable. Further, the heat conductive composition according to the present technology may contain at least one of aluminum nitride, metal hydroxide, metal oxide and carbon fiber as the heat conductive filler.
  • the metal hydroxide and the metal oxide examples include aluminum hydroxide, alumina, aluminum nitride, magnesium oxide and the like.
  • the heat conductive filler only alumina, only aluminum nitride, or only carbon fibers may be used.
  • the heat conductive composition according to the present technology preferably contains at least aluminum nitride as a heat conductive filler from the viewpoint of flame retardancy and heat conductivity, and contains aluminum nitride, alumina, and magnesium oxide. It is more preferable to use a mixture, and a mixture containing carbon fibers further may be used.
  • the content of the heat conductive filler in the heat conductive composition can be appropriately determined according to the desired thermal conductivity and the like, and the volume content in the heat conductive composition can be set to, for example, 80 to 90 volumes. Can be%.
  • the content of the heat conductive filler in the heat conductive composition is less than 80% by volume, it tends to be difficult to obtain sufficient thermal conductivity. Further, when the content of the heat conductive filler in the heat conductive composition exceeds 90% by volume, it tends to be difficult to fill the heat conductive filler.
  • the content of the heat conductive filler in the heat conductive composition can be 83% by volume or more, 84% by volume or more, 85% by volume or more, and 83 to 85%. It can also be% by volume. When two or more kinds of thermally conductive fillers are used in combination, it is preferable that the total amount satisfies the above range of contents.
  • the content of aluminum nitride in the heat conductive filler can be 1 to 100% by volume.
  • the thermally conductive composition contains an alkoxysilane compound.
  • the alkoxysilane compound is hydrolyzed with, for example, the amount of water contained in the heat conductive filler, binds to the heat conductive filler, and contributes to the dispersion of the heat conductive filler. do.
  • the alkoxysilane compound is a compound having a structure in which 1 to 3 of the four bonds of the silicon atom (Si) are bonded to an alkoxy group and the remaining bonds are bonded to an organic substituent.
  • alkoxy group contained in the alkoxysilane compound examples include a methoxy group, an ethoxy group, a protoxy group, a butoxy group, a pentoxy group, and a hexatoxy group.
  • the alkoxysilane compound is preferably an alkoxysilane compound having a methoxy group or an ethoxy group from the viewpoint of availability.
  • the number of alkoxy groups contained in the alkoxysilane compound is preferably two or more, and more preferably three (trialkoxysilane), from the viewpoint of further enhancing the affinity with the heat conductive filler as an inorganic substance.
  • at least one selected from a trimethoxysilane compound and a triethoxysilane compound is preferable.
  • the functional groups contained in the organic substituents of the alkoxysilane compound are, for example, an acryloyl group, an alkyl group, a carboxyl group, a vinyl group, a methacrylic group, an aromatic group, an amino group, an isocyanate group, an isocyanurate group, an epoxy group and a hydroxyl group.
  • Examples include a group and a mercapto group.
  • an addition reaction type organopolysiloxane containing a platinum catalyst is used as the precursor of the above-mentioned addition reaction type silicone resin, it is preferable that the alkoxysilane compound does not easily affect the curing reaction of the organopolysiloxane. ..
  • the organic substituent of the alkoxysilane compound does not contain an amino group, an isocyanate group, an isocyanurate group, a hydroxyl group, or a mercapto group. Is preferable.
  • an alkylalkoxysilane compound having an alkyl group bonded to a silicon atom that is, an alkyl group-containing alkoxysilane compound.
  • the number of carbon atoms of the alkyl group bonded to the silicon atom is preferably 4 or more, and may be 6 or more, 8 or more, or 10 or more. ..
  • the number of carbon atoms of the alkyl group bonded to the silicon atom in the alkyl group-containing alkoxysilane compound is preferably 16 or less, and may be 14 or less. , 12 or less.
  • the alkyl group bonded to the silicon atom may be linear, branched, or cyclic.
  • the alkoxysilane compound may be used alone or in combination of two or more.
  • Specific examples of the alkoxysilane compound include a vinyl group-containing alkoxysilane compound, an acryloyl group-containing alkoxysilane compound, a methacrylic group-containing alkoxysilane compound, an aromatic group-containing alkoxysilane compound, and an amino group-containing compound, in addition to the alkyl group-containing alkoxysilane compound.
  • Examples thereof include an alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, an isocyanurate group-containing alkoxysilane compound, an epoxy group-containing alkoxysilane compound, and a mercapto group-containing alkoxysilane compound.
  • alkyl group-containing alkoxysilane compound examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and n-propyltri.
  • alkyl group-containing alkoxysilane compounds isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxy
  • At least one selected from silane and hexadecyltrimethoxysilane is preferable, and at least one of n-decyltrimethoxysilane and hexadecyltrimethoxysilane is more preferable.
  • Examples of the vinyl group-containing alkoxysilane compound include vinyltrimethoxysilane and vinyltriethoxysilane.
  • Examples of the acryloyl group-containing alkoxysilane compound include 3-acryloyloxypropyltrimethoxysilane.
  • Examples of the methacryl group-containing alkoxysilane compound include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • aromatic group-containing alkoxysilane compound examples include phenyltrimethoxysilane and phenyltriethoxysilane.
  • amino group-containing alkoxysilane compound examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltri. Examples thereof include methoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.
  • Examples of the isocyanate group-containing alkoxysilane compound include 3-isocyanatepropyltriethoxysilane.
  • Examples of the isocyanurate group-containing alkoxysilane compound include tris- (trimethoxysilylpropyl) isocyanurate.
  • epoxy group-containing alkoxysilane compound examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycid. Examples thereof include xipropyltriethoxysilane.
  • Examples of the mercapto group-containing alkoxysilane compound include 3-mercaptopropyltrimethoxysilane.
  • the thermally conductive composition according to the present technology preferably contains an arcosixylan compound having a melting point of ⁇ 40 ° C. or higher and a boiling point of 100 ° C. or higher.
  • the boiling point of the alcoholicylan compound is 100 ° C. or higher, it is possible to more effectively suppress the vaporization of the alkoxysilane compound at room temperature, and as a result, the heat conductive sheet becomes too hard due to condensation or the like. It can be prevented more reliably.
  • "normal temperature” means a range of 15 to 25 ° C. specified in JIS K0050: 2019 (general rule of chemical analysis method). Further, when the melting point of the alkoxysilane compound is ⁇ 40 ° C.
  • the upper limit of the boiling point of the alcoholicylan compound is not particularly limited, and the higher the boiling point, the more preferable.
  • Examples of alcoholicylan compounds having a melting point of ⁇ 40 ° C. or higher and a boiling point of 100 ° C. or higher include decyltrimethoxysilane, hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-dodecyltrimethoxysilane, and the like.
  • thermally conductive composition examples thereof include n-dodecyltriethoxysilane and hexyltrimethoxysilane.
  • decyltrimethoxysilane and hexadecyltrimethoxysilane in combination.
  • the content of the alkoxysilane compound can be, for example, 50 parts by mass or more, or 100 parts by mass or more. , 200 parts by mass or more, 300 parts by mass or more, 350 parts by mass or more, 400 parts by mass or more, 500 parts by mass or more. , 600 parts by mass or more can be used.
  • the upper limit of the content of the alkoxysilane compound can be, for example, 750 parts by mass or less, and 700 parts by mass or less. It can also be 650 parts by mass or less.
  • the content of the alkoxysilane compound in the heat conductive composition is not particularly limited, and may be, for example, 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the heat conductive filler. , 0.2 to 2.0 parts by mass. When two or more kinds of alkoxysilane compounds are used in combination, it is preferable that the total amount satisfies the above range of contents.
  • the mass ratio of decyltrimethoxysilane to hexadecyltrimethoxysilane is , 100: 98 to 100: 201 are preferable.
  • the thermally conductive composition according to the present technology contains a siloxane-modified acrylic resin.
  • the siloxane-modified acrylic resin is a (meth) acrylic acid ester having one or more polydimethylsiloxane structure (-(CH 3 ) 2 SiO) n- ; n is an integer of 1 or more) and a (meth) acrylic acid alkyl ester. It is a copolymer with.
  • the siloxane-modified acrylic resin is a component for softening the sheet obtained from the thermally conductive composition.
  • the siloxane-modified acrylic resin can further improve the dispersibility of the thermally conductive filler in the thermally conductive composition as compared with, for example, silicone oil.
  • Examples of the (meth) acrylic acid ester having one or more polydimethylsiloxane structures include dimethicone methacrylate.
  • Examples of the (meth) acrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylhexyl acrylate, tridecylic acrylate, and stearyl acrylate.
  • siloxane-modified acrylic resin examples include stearyl-modified acrylate silicone (a copolymer of acrylate, stearyl acrylate and dimethicone methacrylate) and behenyl-modified acrylate silicone (a copolymer of acrylate, behenyl acrylate and dimethicone methacrylate). ), Ethylhexyl-modified acrylate silicone (a copolymer of acrylate, ethylhexyl acrylate and dimethicone methacrylate) and the like.
  • the siloxane-modified acrylic resin may have a hydrophilic functional group such as a carboxy group, an epoxy group, a carbonyl group, a hydroxyl group, or an ether group.
  • the thermally conductive composition according to the present technology preferably contains a siloxane-modified acrylic resin having a melting point of 55 ° C. or lower, and may contain a siloxane-modified acrylic resin having a melting point in the range of 0 to 45 ° C. More preferred.
  • the melting point of the siloxane-modified acrylic resin is 55 ° C or lower, flexibility is exhibited in the actual use range, and it becomes easier to adhere to semiconductor chips such as ICs, CPUs (Central Processing Units), and APs (application processors).
  • the lower limit of the melting point of the siloxane-modified acrylic resin is not particularly limited, but is preferably 25 ° C. or higher, for example.
  • the melting point of the siloxane-modified acrylic resin is 25 ° C or higher, the siloxane-modified acrylic resin becomes a solid at room temperature, and the siloxane-modified acrylic resin becomes a liquid by heating. It can be further improved.
  • siloxane-modified acrylic resins include KP-541, KP-543, KP-545, KP-545L, KP-550, KP-561P, KP-562P, KP-574, and KP-578 (above, Shin-Etsu Silicone). (Manufactured by Toagosei Co., Ltd.), Cymac (registered trademark) US-350 (manufactured by Toagosei Co., Ltd.) and the like.
  • KP-561P and KP-562P are preferable, and KP-561P is more preferable, from the viewpoint of having a melting point of 55 ° C. or lower.
  • the siloxane-modified acrylic resin may be used alone or in combination of two or more. Further, two or more kinds of siloxane-modified acrylic resins having a melting point of 55 ° C. or lower may be used in combination.
  • the content of the siloxane-modified acrylic resin can be, for example, 50 parts by mass or more, or 100 parts by mass or more. It can be 200 parts by mass or more, 300 parts by mass or more, or 350 parts by mass or more. Further, when the content of the organopolysiloxane in the heat conductive composition is 100 parts by mass, the upper limit of the content of the siloxane-modified acrylic resin can be, for example, 500 parts by mass or less, and 450 parts by mass. It can be as follows, or it can be 400 parts by mass or less.
  • the lower limit of the content of the siloxane-modified acrylic resin can be, for example, 0.1 part by mass or more with respect to 100 parts by mass of the heat conductive filler, or 0.3 part by mass or more. It may be 1 part by mass or more.
  • the upper limit of the content of the siloxane-modified acrylic resin can be, for example, 10 parts by mass or less, 7 parts by mass or less, or 5 parts by mass with respect to 100 parts by mass of the heat conductive filler. It may be less than 2 parts by mass, less than 2 parts by mass, or less than 1 part by mass. When two or more kinds of siloxane-modified acrylic resins are used in combination, it is preferable that the total amount satisfies the above range of contents.
  • the thermally conductive resin composition according to the present technology may further contain an antioxidant in addition to the above-mentioned components from the viewpoint of further enhancing the effect of the present technology.
  • an antioxidant for example, a hindered phenolic antioxidant may be used, or a hindered phenolic antioxidant and a thiol-based antioxidant may be used in combination.
  • the hindered phenolic antioxidant for example, captures radicals (peroxy radicals) and effectively contributes to the suppression of oxidative deterioration of organopolysiloxane (addition reaction type silicone resin).
  • a thiol-based antioxidant effectively contributes by decomposing hydrooxide radicals and suppressing oxidative deterioration of organopolysiloxane (addition reaction type silicone resin).
  • hindered phenolic antioxidant examples include those having a structure represented by the following formula 1 as a hindered phenol skeleton.
  • the hindered phenolic antioxidant preferably has one or more skeletons represented by the following formula 1, and may have two or more skeletons represented by the following formula 1.
  • R 1 and R 2 represent a t-butyl group and R 3 represents a hydrogen atom (hindered type)
  • R 1 represents a methyl group
  • R 2 represents a t-butyl group
  • R 3 represents a hydrogen atom (semi-hindered type)
  • R 1 represents a hydrogen atom
  • R 2 represents a t-butyl group
  • R 3 represents a methyl group (less hindered type).
  • a semi-hindered type or a hindered type is preferable.
  • the hindered phenolic antioxidant has three or more skeletons represented by the above formula 1 in one molecule, and the three or more skeletons represented by the formula 1 are hydrocarbon groups or. , It is preferable that the structure is linked by a group consisting of a hydrocarbon group and a combination of —O— and —CO—.
  • the hydrocarbon group may be linear, branched or cyclic.
  • the number of carbon atoms of the hydrocarbon group can be, for example, 3 to 8.
  • the molecular weight of the hindered phenolic antioxidant can be, for example, 300 to 850, or 500 to 800.
  • the hindered phenolic antioxidant may have an ester bond in its structure.
  • examples of such phenolic antioxidants include stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis [3- (3', 5'-di-t-butyl-).
  • phenolic antioxidants include Adekastab AO-30, Adekastab AO-50, Adekastab AO-60, Adekastab AO-80 (above, manufactured by ADEKA), Irganox 1010, Irganox 1035, Irganox 1076, Ilganox 1135 (above, manufactured by BASF) and the like can be mentioned.
  • the phenolic antioxidant may be used alone or in combination of two or more.
  • the lower limit of the content of the phenolic antioxidant can be, for example, 0.1 part by mass or more, or 0.5 part by mass or more with respect to 100 parts by mass of the organopolysiloxane.
  • the upper limit of the content of the phenolic antioxidant may be, for example, 10 parts by mass or less with respect to 100 parts by mass of the organopolysiloxane, and may be 5 parts by mass or less.
  • thiol-based antioxidant examples include a type having a thioether skeleton and a type having a hindered phenol skeleton.
  • examples of the thiol-based antioxidant include ditridecyl 3,3'-thiobispropionic acid, tetrakis [3- (dodecylthio) propionic acid] pentaerythritol, and 4,6-bis (octylthiomethyl) -o-cresol. Can be mentioned.
  • thiol-based antioxidants include ADEKA STAB AO-412S, ADEKA STAB AO-503, ADEKA STAB AO-26 (above, manufactured by ADEKA), Sumilyzer TP-D (manufactured by Sumitomo Chemical), and Irganox1520L (manufactured by BASF Japan). ) And so on.
  • thiol-based antioxidants tetrakis [3- (dodecylthio) propionic acid] pentaerythritol (commercially available: Adecastab AO-412S, Sumitomo Chemical Co., Ltd.), Irganox 1520L is preferable.
  • the thiol-based antioxidant may be used alone or in combination of two or more.
  • the content of the thiol-based antioxidant in the heat conductive composition may be about the same as that of the phenol-based antioxidant, or may be higher than that of the phenol-based antioxidant.
  • the lower limit of the content of the thiol-based antioxidant can be, for example, 0.1 part by mass or more with respect to 100 parts by mass of the organopolysiloxane.
  • the upper limit of the content of the thiol-based antioxidant may be, for example, 20 parts by mass or less, or 10 parts by mass or less, with respect to 100 parts by mass of the organopolysiloxane.
  • the thermally conductive composition according to the present technology contains an organopolysiloxane, a thermally conductive filler, an alkoxysilane compound, and a siloxane-modified acrylic resin.
  • the synergistic effect can improve the thermal conductivity and flexibility when the thermally conductive composition is made into a thermally conductive sheet.
  • the heat conductive composition according to the present technology has heat conductivity and flexibility when formed into a sheet even if the heat conductive filler contains 80 to 90% by volume of the heat conductive filler. Can be good.
  • the thermally conductive composition according to the present technology may further contain components other than the above-mentioned components as long as the effects of the present technology are not impaired.
  • the thermally conductive composition may further contain a heavy metal inactivating agent for the purpose of improving the deterioration resistance of the thermally conductive sheet.
  • the heavy metal deactivating agent include the ADEKA STAB ZS series (such as ADEKA STAB ZS-90) manufactured by ADEKA.
  • the thermally conductive composition according to the present technology can be obtained, for example, by kneading each of the above-mentioned components using a kneader (planetary kneader, ball mill, Henschel mixer, etc.).
  • a kneader planetary kneader, ball mill, Henschel mixer, etc.
  • the required amount of the heat conductive filler is not mixed at once with the main agent, the curing agent and the heat conductive filler.
  • the main agent and the curing agent may be divided and mixed separately, and the component containing the main agent and the component containing the curing agent may be mixed at the time of use.
  • FIG. 1 is a cross-sectional view showing an example of a heat conductive sheet.
  • the heat conductive sheet 1 is made of a cured product of the above-mentioned heat conductive composition.
  • the heat conductive sheet 1 is desired to have a heat conductive composition on a release film 11 formed of, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyolefin, polymethylpentene, glassin paper, or the like. It is obtained by curing the organopolysiloxane, which is a binder resin, by applying it to the thickness of the above and heating it.
  • the thickness of the heat conductive sheet 1 (thickness of the sheet body excluding the release film 11) can be appropriately selected depending on the intended purpose, and can be, for example, 0.05 to 5 mm.
  • the thermal conductive sheet 1 can have a thermal conductivity of 3.5 W / m ⁇ K or more, and can also have a thermal conductivity of 4.0 W / m ⁇ K or more. , 4.5 W / m ⁇ K or more, 5.0 W / m ⁇ K or more, 6.0 W / m ⁇ K or more, 7.0 W / m ⁇ K or more It can be more than 7.5 W / m ⁇ K or more.
  • the upper limit of the thermal conductivity of the thermal conductivity sheet 1 is not particularly limited, but can be, for example, 12.0 W / m ⁇ K or less, 11.0 W / m ⁇ K or less, and 9 It can also be set to 0.0 W / m ⁇ K or less.
  • the method for measuring the thermal conductivity is the same as in the examples described later.
  • the thermal resistance sheet 1 can have a thermal resistance value of 1.0 ° C. cm 2 / W or less, 0.9 ° C. cm 2 / W or less, and 0.7 ° C. ⁇ . It can be cm 2 / W or less, 0.5 ° C. cm 2 / W or less, 0.3 ° C. cm 2 / W or less, 0.2 ° C. cm 2 or less. It can also be less than / W.
  • the lower limit of the thermal resistance value of the heat conductive sheet 1 is not particularly limited, but may be, for example, 0.01 ° C. cm 2 / W or more. The method for measuring the thermal resistance value is the same as in the examples described later.
  • the thermal conductivity sheet 1 can have a thermal conductivity retention rate of 70% or more, which is 75% or more, as shown by the following formula 2 when aged at 200 ° C. for 24 hours, for example. It can be 80% or more, or 90% or more. Equation 2: (Thermal conductivity of the heat conductive sheet after the aging treatment / The thermal conductivity of the heat conductive sheet before the aging treatment) ⁇ 100
  • the heat conductive sheet 1 uses the above-mentioned heat conductive composition, it has good flexibility.
  • the compressibility heat conductivity
  • the ratio of the amount of change from the initial thickness of the sheet) divided by the initial thickness of the heat conductive sheet, that is, the compressibility represented by the following formula 3 can be 60% or more, and can be 70% or more. It can be 80% or more.
  • the heat conductive sheet 1 is made of the above-mentioned heat conductive composition, due to the synergistic effect of the organopolysiloxane, the heat conductive filler, the alkoxysilane compound, and the siloxane modified acrylic resin, It has good thermal conductivity and flexibility, and in particular, even those made of a thermally conductive composition containing 80 to 90% by volume of a thermally conductive filler have good thermal conductivity and flexibility. Further, since the heat conductive sheet 1 has a small repulsion against compression and the sheet itself is softened by heat, it has good adhesion to, for example, a heat generating element or a heat radiating body. That is, the heat conductive sheet 1 has high followability to the heat generating element and the radiator.
  • the heat conductive sheet 1 has good heat conductivity and flexibility, it can be applied to a heat dissipation structure in which the heat conductive sheet 1 is sandwiched between a heating element and a heat radiation member.
  • the heating element include integrated circuit elements such as CPUs, GPUs (Graphics Processing Units), DRAMs (Dynamic Random Access Memory), flash memories, transistors, resistors, and other electronic components that generate heat in electric circuits.
  • the heating element also includes a component that receives an optical signal such as an optical transceiver in a communication device.
  • the heat radiating member may be a member that conducts heat generated from a heating element and dissipates it to the outside.
  • a heat sink, a heat spreader, or the like which is used in combination with an integrated circuit element, a transistor, an optical transceiver housing, or the like.
  • the heat radiating member include a radiator, a cooler, a die pad, a printed circuit board, a cooling fan, a Pelche element, a heat pipe, a metal cover, a housing, and the like.
  • FIG. 2 is a cross-sectional view showing an example of a semiconductor device.
  • the heat conductive sheet 1 from which the release film 11 has been peeled off can be mounted inside an electronic component such as a semiconductor device or various electronic devices.
  • the heat conductive sheet 1 is mounted on a semiconductor device 50 built in various electronic devices and is sandwiched between a heating element and a heat radiating member. That is, the electronic device includes a heating element, a heat radiating member, and a heat conductive sheet 1 arranged between the heating element and the heat radiating member.
  • the second has at least an electronic component 51, a heat spreader 52, and a heat conductive sheet 1, and the heat conductive sheet 1 is sandwiched between the heat spreader 52 and the electronic component 51.
  • the semiconductor device 50 has high heat dissipation.
  • the heat conductive sheet 1 is sandwiched between the heat spreader 52 and the heat sink 53 to form a heat radiating member that dissipates heat of the electronic component 51 together with the heat spreader 52.
  • the mounting location of the heat conductive sheet 1 is not limited to between the heat spreader 52 and the electronic component 51 and between the heat spreader 52 and the heat sink 53, and can be appropriately selected depending on the configuration of the electronic device or the semiconductor device.
  • Articles having such a heat dissipation structure include, for example, ECUs used for controlling electrical components such as personal computers, server devices, mobile phones, radio base stations, engines of transportation machines such as automobiles, power transmission systems, steering systems, and air conditioners. (Electronic Control Unit) can be mentioned.
  • thermally conductive composition composed of the raw materials shown in Table 1 was obtained.
  • the dispersibility of this thermally conductive composition was evaluated.
  • each evaluation shown in Table 1 was performed on the heat conductive sheet obtained from the heat conductive composition.
  • the present technology is not limited to the following examples.
  • Silicone resin A (Product name: CY52-276A, manufactured by Toray Dow Corning) Silicone resin B (Product name: CY52-276B, manufactured by Toray Dow Corning) Graft copolymer composed of acrylic polymer and dimethylpolysiloxane (product name: KP-561P, melting point 25-35 ° C, manufactured by Shinetsu Silicone Co., Ltd.) Graft copolymer composed of acrylic polymer and dimethylpolysiloxane (product name: KP-578, melting point 55 ° C or less, manufactured by Shin-Etsu Silicone Co., Ltd.) Polyglycerin-modified silicone surfactant with branched silicone chains (Product name: KF-6106, manufactured by Shinetsu Silicone Co., Ltd.) Alkoxytrialkoxysilane: Hexadecyltrimethoxysilane (Product name: Dynasylan 9116 (melting point 1 ° C, boiling point 155 ° C), manufactured by
  • Examples 1 to 5 Comparative Examples 1 and 2>
  • the heat conductive filler a mixture of aluminum nitride and alumina or a mixture of aluminum nitride, alumina and magnesium oxide was used.
  • the mixing amount is about 10640 parts by mass of aluminum nitride and about 1880 parts by mass of alumina with respect to 100 parts by mass of the silicone resin, one by one for the silicone resin. It was stirred each time it was added.
  • the mixing amount was about 4220 parts by mass of aluminum nitride and about 2800 parts by mass of alumina with respect to 100 parts by mass of the silicone resin.
  • the amount of magnesium oxide was about 4980 parts by mass, and the mixture was stirred each time it was added to the silicone resin one by one.
  • the total mixing amount of aluminum nitride, alumina and magnesium oxide is about 8000 parts by mass (aluminum nitride) with respect to 100 parts by mass of the silicone resin.
  • the mixture was stirred each time it was added to the silicone resin one by one.
  • a planetary stirrer was used for stirring, and the rotation speed was set to 1200 rpm.
  • the heat conductive composition was applied onto a release film (material: PET, thickness 125 ⁇ m) so as to have a thickness of 2 mm or 1.5 mm, and then a cover film (material) to which a release agent was applied. : PET, thickness 50 ⁇ m) was covered and heated at 80 ° C. for 6 hours to obtain a heat conductive sheet.
  • the heat conductive filler was added one by one to the heat conductive composition in which the components excluding the heat conductive filler were mixed, and the mixture was stirred.
  • a commercially available rotation / revolution stirrer (rotational vacuum stirring defoaming mixer (device name: V-mini 300, manufactured by EME) was used for stirring, and the rotation speed was set to 1200 rpm.
  • the time required for the conductive filler to disperse was visually evaluated. The results are shown in Table 1.
  • Thermal resistance value Using a thermal resistance measuring device compliant with ASTM-D5470, the thermal resistance value (° C. cm 2 / W) of the heat conductive sheet was measured by applying a load of 1 kgf / cm 2 . Practically, the thermal resistance value is preferably 1.0 (° C. cm 2 / W) or less. The results are shown in Table 1.
  • Heat stability Is the shape of the heat conductive sheet maintained and the oil bleeding is minimal when the heat conductive sheet is cut to a thickness of 2 mm and 30 mm ⁇ 30 mm and aged at 200 ° C for 24 hours (super accelerated test)? Please evaluate (heat stability). When there is no shape change and the oil bleed is within 1 mm, the heat resistance stability is evaluated as " ⁇ ”, and when the shape is slightly deformed but the oil bleed is within 1 mm, the heat resistance stability is evaluated as " ⁇ " and the shape is The heat stability was evaluated as "x" when it was significantly deformed or when it did not correspond to " ⁇ ” or " ⁇ ”. Practically, it is preferable that the evaluation of heat resistance stability is " ⁇ " or " ⁇ ". The results are shown in Table 1.
  • Examples 1 to 5 when the organopolysiloxane, the heat conductive filler, the alkoxysilane compound, and the siloxane-modified acrylic resin are contained, and the content of the organopolysiloxane is 100 parts by mass, the alkoxysilane compound is used. Since the heat conductive composition having a total content of 100 parts by mass or more of the siloxane-modified acrylic resin was used, it was found that a heat conductive sheet having good initial thermal conductivity and softness (flexibility) could be obtained. ..

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Abstract

L'invention concerne : une composition thermoconductrice à partir de laquelle une feuille thermoconductrice ayant une conductivité thermique et une flexibilité satisfaisantes peut être formée ; et une feuille thermoconductrice produite à l'aide de la composition thermoconductrice. Cette composition thermoconductrice comprend un organopolysiloxane, une charge thermoconductrice, un composé alcoxy silane et une résine acrylique modifiée par siloxane, la teneur totale du composé alcoxy silane et de la résine acrylique modifiée par siloxane étant, lorsque la teneur de l'organopolysiloxane est définie comme 100 parties en masse, de 100 parties en masse ou plus. La feuille thermoconductrice comprend un produit durci de la composition thermoconductrice.
PCT/JP2021/028782 2020-08-26 2021-08-03 Composition thermoconductrice et feuille thermoconductrice l'utilisant WO2022044723A1 (fr)

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WO2023162636A1 (fr) * 2022-02-28 2023-08-31 信越化学工業株式会社 Composition de silicone thermoconductrice

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11209618A (ja) * 1998-01-27 1999-08-03 Matsushita Electric Works Ltd 熱伝導性シリコーンゴム組成物
WO2017002474A1 (fr) * 2015-07-01 2017-01-05 昭和電工株式会社 Composition de résine de silicone thermodurcissable contenant du nitrure de bore, dispersant pour compositions de résine de silicone et charge inorganique
WO2017051738A1 (fr) * 2015-09-25 2017-03-30 信越化学工業株式会社 Composition de graisse de silicone thermoconductrice et thermoadoucissante, procédé de formation de film thermoconducteur, structure de dissipation de chaleur et dispositif de module de puissance
JP2020073626A (ja) * 2019-08-01 2020-05-14 昭和電工株式会社 無機粒子分散樹脂組成物及び無機粒子分散樹脂組成物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11209618A (ja) * 1998-01-27 1999-08-03 Matsushita Electric Works Ltd 熱伝導性シリコーンゴム組成物
WO2017002474A1 (fr) * 2015-07-01 2017-01-05 昭和電工株式会社 Composition de résine de silicone thermodurcissable contenant du nitrure de bore, dispersant pour compositions de résine de silicone et charge inorganique
WO2017051738A1 (fr) * 2015-09-25 2017-03-30 信越化学工業株式会社 Composition de graisse de silicone thermoconductrice et thermoadoucissante, procédé de formation de film thermoconducteur, structure de dissipation de chaleur et dispositif de module de puissance
JP2020073626A (ja) * 2019-08-01 2020-05-14 昭和電工株式会社 無機粒子分散樹脂組成物及び無機粒子分散樹脂組成物の製造方法

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