EP4504843A1 - Composition de silicone thermoconductrice - Google Patents

Composition de silicone thermoconductrice

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Publication number
EP4504843A1
EP4504843A1 EP22936183.7A EP22936183A EP4504843A1 EP 4504843 A1 EP4504843 A1 EP 4504843A1 EP 22936183 A EP22936183 A EP 22936183A EP 4504843 A1 EP4504843 A1 EP 4504843A1
Authority
EP
European Patent Office
Prior art keywords
thermally conductive
component
conductive silicone
silicone composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22936183.7A
Other languages
German (de)
English (en)
Other versions
EP4504843A4 (fr
Inventor
Dan Li
Ling Shen
Hengda YU
Xingyu Zhu
Wenting GAO
Yongming Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP4504843A1 publication Critical patent/EP4504843A1/fr
Publication of EP4504843A4 publication Critical patent/EP4504843A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a thermally conductive silicone composition, and particularly relates to a thermally conductive silicone composition exhibiting good flowability, as well as high thermal conductivity when cured, the preparation method and use thereof.
  • Thermally conductive silicone compositions exhibiting good flowability and high thermal conductivity is widely used in electronic devices, especially the telecom and datacom devices, such as 5G station, or the like.
  • thermally conductive silicone compositions may be exemplified by the following: a thermally conductive silicone composition comprising an organopolysiloxane having vinyl groups, an organohydrogenpolysiloxane, a thermally conductive filler, an adhesion-imparting agent selected from epoxy silane or alkyl titanate, and a platinum-type catalyst.
  • a thermally conductive silicone composition comprising an organopolysiloxane having vinyl groups, an organohydrogenpolysiloxane, a thermally conductive filler, an adhesion-imparting agent selected from epoxy silane or alkyl titanate, and a platinum-type catalyst.
  • the compositions In order to improve thermal conductivity in a cured body obtained from such thermally conductive silicone compositions, the compositions must incorporate a large amount of thermally conductive fillers. However, an increase of the amount of such fillers impairs flowability of the composition.
  • JP 2003301189 A discloses an invention of a heat dissipating silicone grease composition, and describes the use of a thermally conductive filler having an average particle size falling within a range of 0.1 to 100 ⁇ m, and preferably 1 to 20 ⁇ m.
  • JP 201013563 A discloses an invention of a thermally conductive silicone grease, and states that (A) a thermally conductive inorganic filler preferably has an average particle size falling within a range of 0.1 to 100 ⁇ m, in particular, 1 to 70 ⁇ m.
  • B-1 a zinc oxide powder (amorphous, average particle size: 1.0 ⁇ m)
  • B-2 an alumina powder (spherical, average particle size: 2.0 ⁇ m)
  • B-3 an aluminum powder (amorphous, average particle size: 7.0 ⁇ m) .
  • US 20180134938 A1 discloses a thermally conductive composition good in thermal conductivity, low in viscosity and easy in application, including (A) a spherical thermally conductive filler and (B) an alkoxysilane compound or dimethylpolysiloxane, wherein the spherical thermally conductive filler of component (A) is a mixture formulated with specific ratios of fillers having different average particle sizes, the mixture being formulated with a spherical thermally conductive filler made of a nitride and having an average particle size of 50 ⁇ m or more in an amount of 30%by mass or more.
  • the thermal conductivity of the above disclosed compositions is no more than 10 W/ (m ⁇ K) , which cannot meet the increasing demand on heat-dissipating performance.
  • thermally conductive silicone composition that has a favorable combination of properties including good flowability (more than 15 g/min at 25 °C) and high thermal conductivity when cured (more than 10 W/ (m ⁇ K) ) .
  • thermally conductive silicone composition comprising:
  • component (D) a thermal conductive filler other than component (C) ;
  • thermoly conductive silicone composition also disclosed herein is the method for preparing a thermally conductive silicone composition according to the present invention.
  • thermoly conductive silicone composition also disclosed herein is the cured product of the thermally conductive silicone composition according to the present invention.
  • thermally conductive silicone composition and the cured product of the thermally conductive silicone composition according to the present invention in manufacturing electronic devices.
  • room temperature refers to a temperature of about 20 °C to about 25 °C, preferably about 25 °C.
  • the present disclosure is generally directed to thermally conductive silicone composition
  • thermally conductive silicone composition comprising:
  • component (D) a thermal conductive filler other than component (C) ;
  • the thermally conductive silicone composition comprises (A) an alkenyl group-containing organopolysiloxane.
  • alkenyl refers to a radical of a straight-chain or branched hydrocarbon group having from 2 to 40 carbon atoms and one or more carbon-carbon double bonds (e.g., 1, 2, 3, or 4 double bonds) ( “C 2-40 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 30 carbon atoms ( “C 2-30 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 20 carbon atoms ( “C 2-20 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 10 carbon atoms ( “C 2-10 alkenyl” ) .
  • an alkenyl group has 2 to 9 carbon atoms ( “C 2-9 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 8 carbon atoms ( “C 2-8 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 7 carbon atoms ( “C 2-7 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 6 carbon atoms ( “C 2-6 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 5 carbon atoms ( “C 2-5 alkenyl” ) .
  • an alkenyl group has 2 to 4 carbon atoms ( “C 2-4 alkenyl” ) . In some embodiments, an alkenyl group has 2 to 3 carbon atoms ( “C 2-3 alkenyl” ) . In some embodiments, an alkenyl group has 2 carbon atoms ( “C 2 alkenyl” ) .
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl) .
  • Examples of C 2- 4 alkenyl groups include ethenyl (C 2 ) , 1-propenyl (C 3 ) , 2-propenyl (C 3 ) , 1-butenyl (C 4 ) , 2-butenyl (C 4 ) , butadienyl (C 4 ) , and the like.
  • Examples of C 2-6 alkenyl groups include the aforementioned C 2- 4 alkenyl groups as well as pentenyl (C 5 ) , pentadienyl (C 5 ) , hexenyl (C 6 ) , and the like.
  • alkenyl examples include heptenyl (C 7 ) , octenyl (C 8 ) , octatrienyl (C 8 ) , and the like.
  • each instance of an alkenyl group is independently unsubstituted (an “unsubstituted alkenyl” ) or substituted (a “substituted alkenyl” ) with one or more substituents.
  • the alkenyl group is an unsubstituted C 2-30 alkenyl.
  • the alkenyl group is a substituted C 2-30 alkenyl.
  • the quantity of alkenyl groups is within a range from 0.01 to 10 wt%, and preferably from 0.1 to 5 wt%based on the total weight of the organopolysiloxane.
  • these alkenyl groups may be bonded to silicon atoms at the terminals of the molecular chain, to non-terminal silicon atoms within the molecular chain, or to both these types of silicon atoms, although from the viewpoints of ensuring a good curing rate for the composition and producing favorable physical properties for the cured product, the organopolysiloxane should comprise at least alkenyl groups bonded to a molecular chain terminal silicon atom, and preferably to the silicon atoms at both terminals of the molecular chain.
  • the viscosity at 25°C of the component (A) is within a range from 10 to 1000 mPa ⁇ s, and preferably from 10 to 500 mPa ⁇ s. If the viscosity at 25°C is within the range defined above, then the physical characteristics of the cured silicone rubber can be improved.
  • the viscosity at 25°C of the component (A) refers to the calculated viscosity according to the following modified Gordon-Taylor equation (I) , that is, these alkenyl group-containing organopolysiloxane as a whole have a calculated viscosity of from 10 to 1000 mPa ⁇ s, and preferably from 10 to 500 mPa ⁇ s, which means that an alkenyl group-containing organopolysiloxane having a viscosity at 25°C of out of the aforementioned range can be used as long as the calculated viscosity as a whole is within the aforementioned range.
  • the calculated viscosity of two or more alkenyl group-containing organopolysiloxane can be calculated according to the following modified Gordon-Taylor equation (I) :
  • W 1 is weight percentage of the first alkenyl group-containing organopolysiloxane based on total weight of alkenyl group-containing organopolysiloxane
  • ⁇ 1 is the viscosity of the first alkenyl group-containing organopolysiloxane
  • W 2 is weight percentage of the second alkenyl group-containing organopolysiloxane based on total alkenyl group-containing organopolysiloxane
  • ⁇ 2 is the viscosity of the second alkenyl group-containing organopolysiloxane
  • W n is weight percentage of the n th alkenyl group-containing organopolysiloxane based on total alkenyl group-containing organopolysiloxane
  • ⁇ n is the viscosity of the n th alkenyl group-containing organopolysiloxane
  • ⁇ is the calculated viscosity of the mixture of the first to
  • the molecular structure of the component (A) including but not limited to straight chain structures, cyclic structures, branched chain structures, partially branched straight chain structures and three-dimensional network structures, although an essentially straight chain diorganopolysiloxane in which the principal chain is formed from repeating diorganosiloxane units, and both terminals of the molecular chain are blocked with triorganosiloxy groups, is preferred.
  • the component (A) may be a single polymer with this type of molecular structure, a copolymer with this type of molecular structure, or a mixture of different polymers with this type of molecular structure.
  • component (A) include the compounds represented by the general formulas (i) to (v) shown as below.
  • R each independently represents a substituted or unsubstituted monovalent hydrocarbon group bonded to a silicon atom, but excluding alkenyl groups, as described above, and is preferably a methyl group or a phenyl group.
  • n is an integer of from 0 to 5000.
  • n is an integer of from 0 to 5000, m is an integer of from 5 to 5000, and n+m ranges from 5 to 10000.
  • n ranges from as little as 0, 10, 50, 100, 200, 500, as great as 1000, 2000, 5000, or within any range defined between any two of the foregoing values; and m ranges from 5, 10, 50, 200, or as great as 500, 1000, 2000, 5000, or within any range defined between any two of the foregoing values.
  • n+m ranges from as little as 5, 10, 30, 50, 100, 200, 500, or great as 1000, 2000, 5000, 10000, or within any range defined between any two of the foregoing values, such as between 10 and 10000, and between 1000 and 5000.
  • the unsubstituted or substituted monovalent hydrocarbon group R in the formulas (i) to (v) above is each independently selected from straight-chain alkyl groups, preferably selected from methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group; branched-chain alkyl groups, branched-
  • component (A) there are no particular restrictions on the molecular weight of component (A) , and preferably in the range of from 3000 to 20,000 g/mol.
  • the component (A) may be used either alone, or in combinations of two or more different compounds.
  • Such alkenyl group-containing organopolysiloxane used as component (A) can be produced using conventionally known methods.
  • the alkenyl group-containing organopolysiloxane is produced by conducting an equilibration reaction of an organocyclooligosiloxane and a hexaorganodisiloxane in the presence of either an alkali or acid catalyst.
  • Examples of commercially available products of the component (A) include RH-Vi100E, RH-Vi322, RH-Vi323 and RH-Vi324 available from Zhejiang Runhe Chemical New Material Co., Ltd.
  • the component (A) is present in an amount of from 0.01%to 5%, preferably 0.05 %to 3%by weight, based on the total weight of the composition.
  • the thermally conductive silicone composition also comprises (B) an organohydrogenpolysiloxane having an average of at least two hydrogen atoms directly bonded to a silicon atom in the molecule, which works as a crosslinking agent to the component (A) to form silicone polymer matrix.
  • the organohydrogenpolysiloxane has two or more -Si-H groups in one molecule.
  • the -Si-H groups in the component (B) and alkenyl groups in the component (A) are added by a hydrosilylation reaction promoted by (F) catalyst described below to generate a three-dimensional network structure having a crosslinked structure.
  • the component (B) may have an average of at least two, and preferably three or more -Si-H groups per molecule, and these -Si-H groups may be positioned at the terminals of the molecular chain, at non-terminal positions, or at both these positions.
  • the organohydrogenpolysiloxane is linear or branched, and in preferred embodiments, the organohydrogenpolysiloxane can be represented by the general formula (vi) :
  • R’ independently represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group excluding aliphatic unsaturated bonds and at least two R’ groups are hydrogen atoms.
  • Index e represents an integer of 1 or more.
  • Suitable examples of the unsubstituted or substituted monovalent hydrocarbon group in the general formula (vi) is each independently selected from straight-chain alkyl groups, preferably selected from methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group; branched-chain alkyl groups, preferably selected from is
  • the functionality content of -Si-H groups in the component (B) is preferably in the range of from 0.1 to 10.0 mmol/g, more preferably from 0.1 to 5.0 mmol/g.
  • the number of moles of the -Si-H groups contained in the component (B) is preferable in an amount that 0.1 to 5.0 times the number of moles of the alkenyl groups derived from the component (A) .
  • component (B) include but not limited to 1, 1, 3, 3-tetramethyldisiloxane, methylhydrogencyclopolysiloxane, cyclic copolymers of methylhydrogensiloxane and dimethylsiloxane, methylhydrogenpolysiloxane with both terminals blocked with trimethylsiloxy groups, copolymers of dimethylsiloxane and methylhydrogensiloxane with both terminals blocked with trimethylsiloxy groups, dimethylpolysiloxane with both terminals blocked with dimethylhydrogensiloxy groups, copolymers of dimethylsiloxane and methylhydrogensiloxane with both terminals blocked with dimethylhydrogensiloxy groups, copolymers of methylhydrogensiloxane and diphenylsiloxane with both terminals blocked with trimethylsiloxy groups, copolymers of methylhydrogensiloxane, diphenylsiloxane and dimethylsiloxan,
  • the component (B) can be produced using conventionally known methods. In a typical production method, octamethylcyclotetrasiloxane and/or tetramethylcyclodisiloxane, and a compound to from the terminal groups such as hexamethyldisiloxane or a compound incorporating a 1, 1'-dihydro-2, 2', 3, 3'-tetramethyldisiloxane unit are subjected to equilibration in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid, at a temperature of -10°C to 40°C.
  • a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid
  • the component (B) is present in an amount of from 0.01%to 5%, preferably 0.05 %to 3%by weight, based on the total weight of the composition.
  • the thermally conductive silicone composition comprises (C) surface-treated diamond particles having a D 50 particle size of more than 70 ⁇ m.
  • the "D 50 particle size" of the surface-treated diamond particles represents a median diameter in a volume-basis particle size distribution curve obtained by measurement with a laser diffraction particle size analyzer.
  • the component (C) has a D 50 particle size of more than 90 ⁇ m, preferably more than 100 ⁇ m. In preferred embodiments, the component (C) has a D 50 particle size of from more than 70 ⁇ m to 200 ⁇ m, preferably from more than 90 ⁇ m to 200 ⁇ m, more preferably from more than 100 ⁇ m to 200 ⁇ m, even more preferably from 110 ⁇ m to 150 ⁇ m.
  • the shape of the component (C) used in the present invention is not particularly limited. They may have spherical, tetrahedral, hexahedral, octahedral, polyhedron or irregular shape.
  • the term "spherical” refers to a shape in which the entire surface is formed from a convex smooth surface.
  • the spheroidicity is, for example, 0.5 or higher, preferably 0.55 or higher and more preferably 0.6 or higher.
  • the spheroidicity is an index indicating being closer to a sphere the nearer the spheroidicity is to 1; and when the spheroidicity is high, such as in polyhedron shape, it increases the contact surfaces therefore easy for heat dissipating, and further when the spheroidicity is close to 1, it becomes easy for the diamond particles to be dispersed in the silicone polymer matrix.
  • the upper limit of the spheroidicity is not especially limited and is 1.
  • the component (C) shall have surface treatment, preferably silane surface treatment.
  • surface treating the diamond particle it becomes easy for the diamond particle to conform to the silicon matrix, and it becomes easy for the diamond particle in a large amount to be homogeneously dispersed in the silicone polymer matrix.
  • the diamond particle is surface treated with a surface treating agent such as a silane compound, an organotitanium compound, an organoaluminum compound or a phosphate compound, and preferably with the silane compound.
  • the amount of the surface treating agent adhered to the diamond particles is, with respect to the weight of diamond particles, for example, from 0.01%to 2%by weight, preferably from 0.02%to 1.5%by weight, more preferably from no less than 0.03%to 1%by weight. If the content of surface treating agent is within the range defined above, the diamond particles will have improved compatibility with other thermal particles.
  • the silane compound to be used for the surface treatment is not especially limited, and examples thereof include alkoxysilanes and chlorosilanes; and the alkoxysilanes are preferable.
  • the diamond particles surface-treated with the silane compound it is easy to conform to the silicon polymer matrix, making it easy for the amount of the diamond particles blended in the thermal conductive composition to be increased.
  • alkoxysilanes examples include alkoxysilanes having a reactive group and alkoxysilanes having no reactive group.
  • the reactive group of the alkoxysilanes having a reactive group is selected, for example, from an epoxy group, a (meth) acryloyl group, an amino group, a vinyl group, a ureido group, a mercapto group and an isocyanate group.
  • alkoxysilanes having an epoxy group examples include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
  • alkoxysilanes having a (meth) acryloyl group examples include 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3-(meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane.
  • silane compounds having an amino group include alkoxysilanes such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.
  • silane compounds having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.
  • alkoxysilanes having a mercapto group examples include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane.
  • alkoxysilanes having a ureido group examples include 3-ureidopropyltrimethoxysilane.
  • alkoxysilanes having an isocyanate group examples include 3-isocyanatopropyltriethoxysilane.
  • alkoxysilanes having no reactive group examples include trialkoxysilanes such as aryltrialkoxysilanes, alkyltrialkoxysilanes, and dialkoxysilanes such as dialkyldialkoxysilanes and diaryldialkoxysilanes, and among these, trialkoxysilanes such as alkyltrialkoxysilanes are preferable.
  • alkyltrialkoxysilanes examples include alkyltrialkoxysilanes in which the number of carbon atoms of the alkyl group is about 1 to 10, such as methyltrimethoxysilane, methyltriethoxysilane, n-proyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane and n-decyltrimethoxysilane.
  • alkyltrialkoxysilanes in which the number of carbon atoms of the alkyl group is about 1 to 10, such as methyltrimethoxysilane, methyltriethoxysilane, n-proyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltrimethoxysilane,
  • aryltrimethoxysilanes include aryltrimethoxysilanes in which the number of carbon atoms of the aryl group is about 6 to 10, such as phenyltrimethoxysilane, benzyltrimethoxy silane and tolyltrimethoxysilane.
  • dialkoxysilanes include dimethyldimethoxysilane and dimethyldiethoxysilane.
  • a polymeric silane compound being a reaction product of an alkoxysilane having a reactive group with a polyorganosiloxane having a functional group reactive with the reactive group.
  • the suitable polymeric silane compound can be obtained, for example, by mixing the alkoxysilane having a reactive group with the polyorganosiloxane and allowing these to react under heating in the presence of a catalyst such as a platinum-based catalyst, a palladium-based catalyst or a rhodium-based catalyst.
  • a catalyst such as a platinum-based catalyst, a palladium-based catalyst or a rhodium-based catalyst.
  • the alkoxysilane having a reactive group the ones listed in the above can be used, but among the above, it is preferable to use triakoxysilanes.
  • silane compounds having a (meth) acryloyl group or a vinyl group are preferable, and trialkoxysilanes having a (meth) acryloyl group are more preferable.
  • a polymeric silane compound can be obtained by a simple method.
  • the polyorganosiloxane having a functional group to be used for the polymeric silane compound may have one functional group or may have two or more functional groups. In the case of having two or more functional groups, two or more molecules of the alkoxysilane having a reactive group may be bonded to one molecule of the polyorganosiloxane.
  • the polyorganosiloxane having a functional group is preferably an organopolysiloxane having hydrosilyl groups (-SiH) .
  • organopolysiloxane having hydrosilyl groups (-SiH) include methylhydrosiloxane-dimethylsiloxane copolymers and methylhydrosiloxane-phenylmethylsiloxane copolymers. These may contain hydrosilyl groups on the terminals, or may not.
  • the weight-average molecular weight of the polyorganosiloxane having a functional group is preferably 800 to 5000 and more preferably 1500 to 4000.
  • the weight-average molecular weight is a value in terms of polystyrene measured by GPC.
  • a method of the surface treatment using the silane compound is not especially limited, and may be a well-known method; and there can be used, for example, a wet treatment method, a dry treatment method or a pretreatment method. In the present invention, among these, the wet treatment method is preferable.
  • the surface treatment can be made, for example, by adding the diamond particles in a solution in which the silane compound is dispersed or dissolved, mixing the mixture, and thereafter heat-treating the mixture to bond or adhere the silane compound to the surface of the diamond particles.
  • the dry treatment method is a method of the surface treatment using no solution, and specifically, is a method in which the diamond particles are mixed with the silane compound and stirred by a mixer or the like, and thereafter heat-treated to bond or adhere the silane compound to the surface of the diamond particles.
  • Suitable commercially available examples of the component (C) are SD-715, SD-715Q, SD-720 and SD-720Q from FoShan ZhanXun Material Co., Ltd; HFD-A, HFD-B and HFD-C from Henan Huifeng Diamond Co., Ltd.
  • the component (C) is present in an amount of from 0.01%to 85%by weight, more preferably from 0.01%to 60%by weight, based on the total weight of the composition.
  • the thermally conductive silicone composition may further comprise a conductive filler different to component (C) , including but not limited to alumina particles, aluminum nitride particles, fumed silica, precipitated silica, fumed titanium oxide and combinations thereof, preferably alumina particles, aluminum nitride particles and combinations thereof.
  • a conductive filler different to component (C) , including but not limited to alumina particles, aluminum nitride particles, fumed silica, precipitated silica, fumed titanium oxide and combinations thereof, preferably alumina particles, aluminum nitride particles and combinations thereof.
  • the component (D) has a D 50 particle size of at least 0.01 ⁇ m but no greater than 100 ⁇ m, and more preferably from 0.01 ⁇ m to 50 ⁇ m.
  • a combination of alumina particles having a D 50 particle size of 0.01 ⁇ m to 5 ⁇ m, preferably 0.1 ⁇ m to 2 ⁇ m, and aluminum nitride particles having a D 50 particle size of 1 ⁇ m to 50 ⁇ m, preferably 2 ⁇ m to 35 ⁇ m used as component (D) in the present invention is preferred.
  • the shape of the component (D) used in the present invention is not particularly limited. They may have spherical, rod-like, needle-like, disc-like, or amorphous shape, preferably spherical shape.
  • the other fillers can be surface treated or non-surface treated. It is preferably to use surface-treated particles as component (D) in the present invention to increase the compatibility with component (C) in silicon polymer matrix.
  • Suitable commercially available examples of the component (D) include alumina particles from AN5, AN20 and AN30 from Suzhou Ginet New Material Technology Co., Ltd; AA04 from Sumitomo Chemical, NSM-1 and BAK-2 from Bestry Performance Materials Co., Ltd., DAM-03 from Denka Corporation.
  • the component (D) is present in an amount of from 0.01%to 85%, preferably from 20%to 70%by weight, based on the total weight of composition.
  • the thermally conductive silicone composition comprises (E) a silane coupling agent.
  • Suitable silane coupling agent which can be used in the present invention, includes, but not limited to, 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, tetraethoxysilane, vinyltriethoxysilane, methyltris (methylethylketoxime) silane, vinyltriacetoxysilane, ethyl orthosilicate and the like.
  • silane coupling examples include 3-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane from Sinopharm and 9116 from Evonik.
  • the component (E) is present in an amount of from 0.1%to 5%by weight, preferably from 0.1%to 3%by weight, based on the total weight of composition. If the quantity falls within this range, then adhesion strength of the cured product derived from the present composition can be improved.
  • the thermally conductive silicone composition comprises (F) a catalyst for accelerating the process of curing, preferably a platinum-based curing catalyst.
  • the component (F) is a catalyst for promoting an addition reaction of an alkenyl group derived from the component (A) , and a -Si-H group derived from the component (B) , and a catalyst well-known as a catalyst used in a hydrosilylation reaction may be used.
  • platinum group metal simple substance such as platinum (including platinum black) , rhodium, and palladium
  • platinum chloride, chloroplatinic acid and chloroplatinate such as H 2 PtCl 4 ⁇ nH 2 O, H 2 PtCl 6 ⁇ nH 2 O, NaHPtCl 6 ⁇ nH 2 O, KaHPtCl 6 ⁇ nH 2 O, Na 2 PtCl 6 ⁇ H 2 O, K 2 PtCl 4 ⁇ nH 2 O, PtCl 4 ⁇ nH 2 O, PtCl 2 , and Na 2 HPtCl 4 ⁇ nH 2 O (here, in the formula, n is an integer of 0 to 6, preferably alcohol-modified chloroplatinic acid) ; complexes of chloroplatinic acid and olefin; ones obtained by supporting a platinum group metal such as platinum black and palladium on a support such as alumina, silica or carbon; a rhodium-olefin
  • Suitable commercially available examples of catalysts include CATALYST 512 from Evonik and CAT-50 available from Avantor.
  • the component (F) is present in an amount of from 1 ppm to 1000 ppm by weight, preferably from 1 ppm to 500 ppm by weight, based on the total weight of the composition.
  • the thermally conductive silicone composition may further optionally comprise additive selected from inhibitors, pigments, dyes, fluorescent dyes, heat resistant additives, flame retardants, plasticizers, adhesion-imparting agents and combinations thereof, provided that the inclusion of these additives does not impair the object of the present invention, curing reaction inhibitor in particularly.
  • inhibitor used in the present invention including but not limited to an acetylene-based compound such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, or 1-ethynyl-1-cyclohexanol; an ene-in compound such as 3-methyl-3-penten-1-in, 3, 5-dimethyl-3-hexen-1-in; a hydrazine-based compound; a phosphine-based compound; or a mercaptan-based compound, in order to regulate the curing rate of the composition, thereby enabling an improvement in the flowability and workability properties.
  • an acetylene-based compound such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, or 1-ethynyl-1-cyclohexanol
  • an ene-in compound such as 3-methyl-3-penten-1-in, 3, 5-dimethyl-3-hexen-1-in
  • Suitable commercially available examples of the inhibitor include Inhibitor MVC from Evonik and 3, 5-dimethyl-1-hexyn-3-ol from Sigma-Aldrich Company.
  • composition of the present invention comprises inhibitor
  • quantity of the inhibitor although a quantity within a range from 0.0001 to 1.0%by weight, based on the total weight of the composition is preferred.
  • the thermally conductive silicone composition based on the total weight of the composition, comprises:
  • component (D) from 0.01%to 85%by weight, preferably from 20%to 70%by weight of a thermal conductive filler other than component (C) ;
  • a further aspect of the present invention relates to a method for preparing a thermally conductive silicone composition by mixing the said components simultaneously at room temperature for such as at least one hour, preferably at least two hours.
  • the thermally conductive silicone composition of the present invention has a good flowability with the thermally conductive filler loading of more than 80%, for example, having a flow rate more than 15 g/min, preferably more than 18 g/min, and more preferably more than 20 g/min defined as the adhesive composition weight dispensed under a pressure of 90 psi per minute using dispenser machine Nordson Ultimus-I equipped with a 30cc plastic tube having a nozzle in a diameter of 2.54 ⁇ 5%mm.
  • Such flow rate, especially more than 15 g/min ensures that the nozzle of conventional adhesive dispensers will not be blocked by the adhesive composition after mixing.
  • the thermally conductive silicone composition can be cured at room temperature for no more than 7 days. Curing can be accelerated by applying heat, for example, by heating from 60 to 200 °C for from 30 minutes to 2 hours.
  • the thermally conductive silicone composition can be applied to the desired substrate by any convenient technique. It can be applied cold or be applied warm if desired. It can be applied by extruding or pasting it onto the substrate or other mechanical application methods such as a caulking gun. Generally, the thermally conductive silicone composition of the present invention is applied to one surface of a pair of substrates, and then the substrates are contacted each other to be bonded together. After application, the adhesive composition of the present invention is cured at room temperature, optionally followed by being curing at elevated temperature.
  • an article comprising a first substrate, a cured adhesive, and a second substrate bonded to the first substrate through the cured adhesive comprising a cured product derived from the curable adhesive composition according to any one of the preceding claims.
  • the first substrate and/or second substrate can be of a single material and a single layer or can include multiple layers of the same or different material.
  • the layers can be continuous or discontinuous.
  • the substrates of the article descried herein can have a variety of properties including rigidity (e.g., rigid substrates (i.e., the substrate cannot be bent by an individual using two hands or will break if an attempt is made to bend the substrate with two hands) , flexibility (e.g., flexible substrates (i.e., the substrate can be bent using no greater than the force of two hands) , porosity, conductivity, lack of conductivity, and combinations thereof.
  • rigidity e.g., rigid substrates (i.e., the substrate cannot be bent by an individual using two hands or will break if an attempt is made to bend the substrate with two hands)
  • flexibility e.g., flexible substrates (i.e., the substrate can be bent using no greater than the force of two hands)
  • porosity e.g., porosity, conductivity, lack of conductivity, and combinations thereof.
  • the substrates of the article can be in a variety of forms including, e.g., fibers, threads, yarns, wovens, nonwovens, films (e.g., polymer film, metallized polymer film, continuous films, discontinuous films, and combinations thereof) , foils (e.g., metal foil) , sheets (e.g., metal sheet, polymer sheet, continuous sheets, discontinuous sheets, and combinations thereof) , and combinations thereof.
  • films e.g., polymer film, metallized polymer film, continuous films, discontinuous films, and combinations thereof
  • foils e.g., metal foil
  • sheets e.g., metal sheet, polymer sheet, continuous sheets, discontinuous sheets, and combinations thereof
  • Useful substrate material used in the present invention include, e.g., polymer (e.g., polycarbonate, ABS resin (Acrylonitrile-Butadiene-Styrene resin) , liquid crystal polymer, polyolefin (e.g., polypropylene, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, and oriented polypropylene, copolymers of polyolefins and other comonomers) , polyether terephthalate, ethylene-vinyl acetate, ethylene-methacrylic acid ionomers, ethylene-vinyl-alcohols, polyesters, e.g.
  • polyethylene terephthalate polycarbonates, polyamides, e.g. Nylon-6 and Nylon-6, 6, polyvinyl chloride, polyvinylidene chloride, cellulosics, polystyrene, and epoxy) , polymer composites (e.g., composites of a polymer and metal, cellulose, glass, polymer, and combinations thereof) , metal (aluminum, copper, zinc, lead, gold, silver, platinum, and magnesium, and metal alloys such as steel (e.g., stainless steel) , tin, brass, and magnesium and aluminum alloys) , carbon-fiber composite, other fiber-based composite, graphene, fillers, glass (e.g., alkali-aluminosilicate toughened glass and borosilicate glass) , quartz, boron nitride, gallium nitride, sapphire, silicon, carbide, ceramic, and combinations thereof, preferably liquid crystal polymer, glass and combinations thereof.
  • polymer composites
  • the cured product of the thermally conductive silicone composition of the present invention has a thermal conductivity of more than 10 W/ (m ⁇ K) , preferably more than 14 W/ (m ⁇ K) measured according to ASTM-D5470.
  • a further aspect in connection with the present invention relates to the use of the thermally conductive silicone composition and the cured product of the thermally conductive silicone composition according to the present invention in manufacturing electronic devices, especially telecom and datacom devices, such as 5G station, or the like.
  • Exemplary electronic devices encompass computers and computer equipment, such as telecom and datacom devices, such as 5G station, or the like; printers, fax machines, scanners, keyboards and the like; medical sensors; automotive sensors and the like; wearable electronic devices (e.g., wrist watches and eyeglasses) , handheld electronic devices (e.g., phones (e.g., cellular telephones and cellular smartphones) , cameras, tablets, electronic readers, monitors (e.g., monitors used in hospitals, and by healthcare workers, athletes and individuals) , watches, calculators, mice, touch pads, and joy sticks) , computers (e.g., desk top and lap top computers) , computer monitors, televisions, media players, household appliances (e.g., refrigerators, washing machines, dryers, ovens, and microwaves) , light bulbs (e.g., incandescent, light emitting diode, and fluorescent) , and articles that include a visible transparent or transparent component, glass housing structures, protective transparent coverings for a display or other optical component.
  • Preferred in accordance with the invention is the use of the embodiments identified earlier on above as being preferred or more preferred, for the thermally conductive silicone composition of the present invention, where preferably two or more of the aspects or corresponding features described for the thermally conductive silicone composition are combined with one another.
  • RH-Vi100E is vinyl terminated polydimethylsiloxane having viscosity of 85 to 115 mPa ⁇ s, manufactured by Zhejiang Runhe Chemical New Material Co., Ltd.
  • Component b is methyl terminated hydrogen branched silicone oil, manufactured Zhejiang Runhe Chemical New Material Co., Ltd.
  • Component e: 9116 is methyltrimethoxysilane, manufactured by Evonik.
  • Component f is a divinyl tetramethyl disiloxane complex having 2%by weight of platinum, manufactured by Evonik.
  • Component g is silicone-based inhibitor manufactured by Evonik.
  • the flow rate of the thermally conductive silicone composition of the present invention and samples of the comparative examples were tested by a dispenser machine (Nordson UltimusTM -I) .
  • the dispenser machine contains a 30cc plastic tube having a nozzle in a diameter of 2.54 ⁇ 5%mm and the tube is connected to a pressurization unit.
  • the sample was dispensed under a pressure of 90psi in 1 minute into a balance tray.
  • the weight of sample dispensed in 1 minute was measured and recorded as flow rate value in Table 1.
  • a larger flow rate value indicates greater flowability for the thermally conductive silicone composition and superior handling characteristics.
  • the flow rate of more than 15 g/min can be acceptable.
  • the thermally conductive silicone composition of the present invention and comparative examples were cured at 125°C for 1 hour.
  • the thermal conductivity of cured samples of the present invention were tested under temperature of 80°C and pressure of 40 psi by LW 9389 manufactured by Longwin according to ASTM-D5470.
  • the thermally conductivity of more than 10 W/ (m ⁇ K) can be acceptable.
  • inventive and comparative thermally conductive silicone adhesive compositions were formed by mixing the components by weight percentage listed in the Table 1 at room temperature for two hours in a 2-liter planetary mixer (manufactured by Rose (Wuxi) Equipment Co., LTD. ) and then cooled down to room temperature.
  • the properties were tested using the methods stated above, and the results of evaluations are shown in Table 1 as below.
  • the thermally conductive silicone adhesives of the present invention showed good flowability and high thermal conductivity when cured.
  • the components of the present invention were not used as in Comparative Examples 1 to 3 (CEx. 1 to CEx. 3) , it showed unsatisfied flow rate compared to the thermally conductive silicone composition of the present invention, indicating that such adhesive compositions may readily cause nozzle blocking of conventional adhesive dispensers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Une composition de silicone thermoconductrice est fournie. La composition comprend : (A) un organopolysiloxane contenant un groupe alcényle ; (B) un organohydrogénopolysiloxane ayant une moyenne d'au moins deux atomes d'hydrogène directement liés à un atome de silicium dans la molécule ; (C) des particules de diamant traitées en surface ayant une taille de particules D50 de plus de 70 µm ; (D) une charge thermoconductrice autre que le composant (C) ; (E) un agent de couplage silane ; et (F) un catalyseur, qui présente une combinaison favorable de propriétés comprenant une bonne aptitude à l'écoulement et une conductivité thermique élevée lorsqu'il est durci.
EP22936183.7A 2022-04-08 2022-04-08 Composition de silicone thermoconductrice Pending EP4504843A4 (fr)

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PCT/CN2022/085861 WO2023193245A1 (fr) 2022-04-08 2022-04-08 Composition de silicone thermoconductrice

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WO2025156249A1 (fr) * 2024-01-26 2025-07-31 Henkel Ag & Co. Kgaa Composition de silicone thermoconductrice
WO2026007059A1 (fr) * 2024-07-04 2026-01-08 Henkel Ag & Co. Kgaa Composition de silicone thermoconductrice

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US4588768A (en) * 1984-10-29 1986-05-13 Sws Silicones Corporation Thermally conductive heat curable organopolysiloxane compositions
CN101139513A (zh) * 2007-10-19 2008-03-12 深圳市金科特种材料股份有限公司 有机硅耐高温导热粘合剂
CN103045158B (zh) * 2013-01-23 2014-12-24 北京海斯迪克新材料有限公司 一种无卤高阻燃性加成型导热硅橡胶胶粘剂
CN104119841B (zh) * 2014-06-30 2017-06-27 中南钻石有限公司 一种金刚石导热膏及其制备方法
CN105199396A (zh) * 2015-10-17 2015-12-30 平湖阿莱德实业有限公司 一种硅胶基碳材料取向型导热界面材料及其生产方法

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