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WO2025030366A1 - Compositions de silicone ignifuges exemptes d'halogène, matériau de stockage de chaleur latente et agent d'enrobage ignifuge - Google Patents

Compositions de silicone ignifuges exemptes d'halogène, matériau de stockage de chaleur latente et agent d'enrobage ignifuge Download PDF

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Publication number
WO2025030366A1
WO2025030366A1 PCT/CN2023/111718 CN2023111718W WO2025030366A1 WO 2025030366 A1 WO2025030366 A1 WO 2025030366A1 CN 2023111718 W CN2023111718 W CN 2023111718W WO 2025030366 A1 WO2025030366 A1 WO 2025030366A1
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WO
WIPO (PCT)
Prior art keywords
retardant
flame
silicone composition
halogen free
free flame
Prior art date
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Pending
Application number
PCT/CN2023/111718
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English (en)
Inventor
Xuedong GAO
Zijia ZHANG
Chen Chen
Jiguang Zhang
Hongyu Chen
Qi Chen
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Dow Global Technologies LLC
Dow Silicones Corp
Original Assignee
Dow Global Technologies LLC
Dow Silicones Corp
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Priority to PCT/CN2023/111718 priority Critical patent/WO2025030366A1/fr
Priority to TW113126873A priority patent/TW202506973A/zh
Publication of WO2025030366A1 publication Critical patent/WO2025030366A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J183/04—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
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • 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
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • 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
    • 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

Definitions

  • the present disclosure relates to a halogen free flame-retardant silicone composition, as well as a latent heat storage material and flame-retardant pottant comprising the halogen free flame-retardant silicone compositions.
  • phase changing adhesive is a new technology that allows for fast charging through phase changing material encapsulated potting material. This technology can keep case temperature cool and safe. And it also brings good user experience while holding. The broader compatibility including such as smartphone, laptop, tablet and electrial vehicals.
  • key element of the potting material is micro-encapsulated Phase Changing Material ( ⁇ PCM) that is added to the potting formulation as a filler, flame retardant will become key barrier for charger application.
  • ⁇ PCM Phase Changing Material
  • Patent Document 1 discloses a heat-conducting and heat-storing multifunctional encapsulating silica gel for battery thermal management, in which the dispersibility of heat-conducting fillers in a silica gel matrix is increased, the heat-conducting property of the heat-conducting and heat-storing multifunctional encapsulating silica gel is improved, and the phase-change microcapsule is added.
  • EG expandable graphite
  • Patent Document 2 discloses a preparation method of a thermally conductive silica gel composite phase change material for a battery thermal management system, and the advantages of simple structure, firm connection, waterproof, dustproof and shockproof performance as well as heat-dissipating and temperature-equalizing functions of batteries are achieved, effective thermal management is performed on heat generation of the batteries and connecting sheets, and thus the batteries are controlled to work in the optimal working temperature range.
  • the FR fillers used are Sb 2 O 3 , Mg (OH) 2 and Al (OH) 3 without N, S and P, and it is trying to avoid N, S and P kinds of typical types of flame-retardant (FR) fillers because of its silica resin system requirements.
  • Patent Document 1 CN108084957
  • Patent Document 2 CN106356588
  • the problem to be solved by the invention is how to improve flame-retardant properties and latent heat storage properties of the halogen free flame-retardant silicone composition comprising organic phase change materials.
  • a novel halogen free flame-retardant silicone composition having a viscosity of lower than 4000cp when the latent heat is equal to or less than 60J/g, or a viscosity of greater than 4000cp when the latent heat increases to 100J/g, as well as a novel latent heat storage material meeting at least one of the following requirements:
  • dielectric strength being close to 10KV/mm, under 500V, 2.00mA, 1mm testing conditions.
  • One aspect of the present invention is a halogen free flame-retardant silicone composition, which comprises:
  • (B) the phase changing encapsulated particle comprises from 30 to 50%by weight, based on the total weight of the halogen free flame-retardant silicone composition.
  • (B) the phase changing encapsulated particle comprises wax particle.
  • (C) the inorganic thermal conductive filler comprises metal hydroxides, metal polyphosphates, ammonium polyphosphate or the combination thereof.
  • (C) the inorganic thermal conductive filler is 6-20 %by weight, based on the total weight of the halogen free flame-retardant silicone composition.
  • (D) the flame-retardant additive filler comprises an intumescent flame retardant.
  • (D) the intumescent flame retardant comprises expandable graphite particles.
  • the expandable graphite particles have a diameter ranging from 200 to 708300 ⁇ m and/or are in amount of from 5 to 12%by weight, based on the total weight of the halogen free flame-retardant silicone composition.
  • the expandable graphite particles are treated with an intercalant material, which is selected from the group consisting of intercalation compounds of SOx and NOx, where x is selected from an integer from 1 to 3.
  • an intercalant material which is selected from the group consisting of intercalation compounds of SOx and NOx, where x is selected from an integer from 1 to 3.
  • the flame-retardant additive filler comprises particles having a particle size in range of 100 microns to 1000 microns.
  • the composition has a viscosity of lower than 4000cp when the latent heat is equal to or less than 60J/g, or a viscosity of greater than 4000cp when the latent heat increases to 100J/g.
  • a second aspect of the present invention is a latent heat storage material prepared by curing the halogen free flame-retardant silicone composition.
  • the material meets at least one of the following requirements:
  • dielectric strength being close to 10KV/mm, under 500V, 2.00mA, 1mm testing conditions.
  • a third aspect of the present invention is a flame-retardant pottant comprising the halogen free flame-retardant silicone composition.
  • the present invention is able to provide a halogen free flame-retardant silicone composition having a viscosity of lower than 4000cp when the latent heat is equal to or less than 60J/g, or a viscosity of greater than 4000cp when the latent heat increases to 100J/g, which can be cured in a time shorter than 30 minutes at 90 °C.
  • the present invention is able to provide a latent heat storage material/flame-retardant pottant meeting at least one of the following requirements:
  • dielectric strength being close to 10KV/mm, under 500V, 2.00mA, 1mm testing conditions.
  • Figure 1 is a Microtek TEM image of the halogen free flame-retardant silicone composition according to the present disclosure.
  • Figure 2 is a schematic image of the halogen free flame-retardant silicone composition according to the present invention.
  • Figure 3 is a schematic image of the expanded graphite according to the present invention.
  • the term “thickness” refers to an average of at least three measurements of a dried sheet (e.g., a sheet having a thickness of 0.2-10.0 mm) as measured using an Ames Gage, Model 13C-B2600 (Ames Corporation Waltham Mass) .
  • polymer or “polymeric” refers, in the alternative, to a polymer made from one or more different monomers, such as a copolymer, a terpolymer, a tetrapolymer, a pentapolymer etc., and may be any of a random, block, graft, sequential or gradient polymer.
  • the halogen free flame-retardant silicone composition comprises, substantially consisting of, or consisting of: (A1) an alkenyl containing siloxane, (A2) a Si-H containing siloxane intermediate; (B) at least one phase changing encapsulated particle; (C) at least one inorganic thermal conductive filler; (D) at least one flame-retardant additive filler; (E) a hydrosilylation reaction catalyst; and optionally, (F) an additive selected from a hydrosilylation catalyst inhibitor, a pigment and an insulant filler.
  • component (A1) is well-known in the art useful as gelling agent; and examples thereof comprises a siloxane containing at least one alkenyl group either at end group or at side group.
  • component (A1) comprises alkenyl endblocked polyorganosiloxanes (i.e., vinyl-terminated PDMS) of the formula:
  • R3 and R4 are selected from the group consisting of alkyl groups having from 1 to 6 carbon atoms per group, phenyl groups, and alkenyl groups with at least 50 percent of R4 being methyl group.
  • the viscosity of component (A1) is from 100 cst to 200000 cst, from 1000 cst to 100000 cst, from 5000 cst to 50000 cst, from 8000 cst to 16000 cst, from 8000 cst to 14000 cst, from 8000 cst to 12000 cst or from 8000 cst to 10000 cst at 25°C.
  • the alkenyl groups contained in component (A1) may comprise from 2 to 14 carbon atoms, 4 to 12 carbon atoms or 6 to 10 carbon atoms; preferably, the alkenyl groups are chosen from the group consisting of vinyl, allyl, hexenyl, decenyl and tetradecenyl, and most preferbly the alkenyl groups are vinyl groups.
  • component (A1) may be incorporated into the curable silicone-based composition in an amount of from 20%to 90%by weight, from 30%to 80%by weight, from 40%to 70%by weight, from 50%to 60%by weight, based on the total amount of the curable silicone-based composition.
  • component (A2) may be used to adjust crosslink density and can be any siloxane intermediates having at least one silicon-bonded hydrogen atoms (i.e., Si-H) per molecule, in some embodiments, having an average of at least two silicon-bonded hydrogen atoms per molecule.
  • the remaining valences of the silicon atoms are satisfied by divalent oxygen atoms or by monovalent alkyl radicals having from 1 to 6 carbon atoms per radical, such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl and phenyl groups.
  • the siloxane intermediates can be homopolymers, copolymers, and mixtures thereof.
  • the siloxane intermediates comprises, but not limited to, a copolymer of trimethylsiloxy and methylhydrogensilicones, or a copolymer of trimethylsiloxy, methylhydrogensilicones and dimethylsilicones.
  • component (A2) is a polymethylhydrogensiloxane having one end blocked by a dimethylhydrogensiloxane unit and another end blocked by a trimethylsiloxane unit, and having an intermediate unit comprising a dimethylsiloxane unit.
  • component (A2) has a SiH content in range of 0.05%to 1.0%, 0.10%to 0.8%, 0.15%to 0.6%or 0.20%to 0.4%.
  • the viscosity of component (A2) is from 1 cst to 500 cst, from 2 cst to 300 cst, from 5 cst to 100 cst, from 10 cst to 80 cst, from 10 cst to 60 cst, from 10 cst to 40 cst or from 10 cst to 20 cst at 25°C.
  • component (A2) is hydrogenated silicone oil having a viscosity 20 cst at 25°C and about 0.77 wt%SiH.
  • component (A2) may be incorporated into the halogen free flame-retardant silicone composition in an amount of from 2%to 20%by weight, from 4%to 16 %by weight, from 6%to 12%by weight, from 8%to 10%by weight, based on the total amount of the halogen free flame-retardant silicone composition.
  • Phase change materials are known as latent heat storage materials that utilize phase change of the materials themselves to passively absorb or release a large amount of heat from surrounding environment.
  • PCM Phase change materials
  • the PMC melts storing the excess thermal energy.
  • the PMC solidifies, releasing the stored thermal energy.
  • component (B) is wax which acts as a phase change material that undergoes a reversible solid-liquid phase change at or below the maximum operating temperatures of electronic devices.
  • Component (B) has a melting point of 30 to 100 °C, preferably 35 to 100 °C, 35 to 80 °C, alternatively 35 to 70 °C. When cooled below its melting point, component (B) solidifies, thereby maintaining intimate contact between heat generating electronic components and heat spreader.
  • melting point (°C) may be measured by a Differential Scanning Calorimeter (DSC) in accordance with ASTM D3418.
  • Exemplary waxes for component (B) include paraffin waxes, microcrystalline waxes, and polyethylene waxes. Preferred waxes are C12-C25 paraffin waxes.
  • the content of component (B) is in a range of from 10 to 75 %by weight, alternatively in a range of from 20 to 65 %by weight, or alternatively in a range of from 30 to 55 %by weight, or alternatively in a range of from 40 to 50 %by weight, each based on a total weight of the halogen free flame-retardant silicone composition. This is because when the content of component (B) is equal to or greater than the lower limit of the range described above, phase change properties of the cured product are good, whereas when the content of component (B) is equal to or less than the upper limit of the range described above, curability of the present composition is good.
  • the halogen free flame-retardant silicone composition comprises at least one inorganic thermal conductive filler.
  • the inorganic thermal conductive filler can be of any filler that has a higher thermal conductivity than polysiloxane matrix.
  • the inorganic thermal conductive fillers can each independently be particles of material selected from a group consisting of aluminum, copper, silver, carbon nanotubes, carbon fiber, graphene, graphite, silicon nitride, boron nitride, aluminum nitride, diamond, silicon carbide, alumina, aluminum trihydrate, zinc oxide, beryllium oxide, magnesium oxide, metal hydroxides, metal polyphosphates, ammonium polyphosphate or the combination thereof.
  • the inorganic thermal conductive fillers can be of any typical size or combination of sizes commonly used in thermally conductive compositions.
  • the inorganic thermal conductive filler is typically 6-30 %by weight, 8-24 %by weight, 10-18 %by weight, 12-15 %by weight, based on the total weight of the halogen free flame-retardant silicone composition.
  • the inorganic thermal conductive filler comprises metal hydroxides, metal polyphosphates, ammonium polyphosphate or the combination thereof.
  • the metal hydroxides e.g., aluminum Trihydrate, ATH
  • ATH aluminum Trihydrate
  • N and P in ammonium polyphosphate (APP) can help catalytic dehydration and decrease smog.
  • component (D) can further improve flame retardancy.
  • the flame retardant fillers are in amount of 1-30 %by weight, 3-24 %by weight, 6-18 %by weight, 8-12 %by weight, based on the total weight of the halogen free flame-retardant silicone composition, which depends on flame retardant requirement of the halogen free flame-retardant silicone composition.
  • the flame-retardant additive filler comprises particles having a particle size in range of 100 microns to 1000 microns, 200 microns to 900 microns, 300 microns to 800 microns, 400 microns to 700 microns, or 500 microns to 600 microns.
  • the flame retardant additive filler comprises non-flammable fibers and sulfur-free carbon black.
  • the non-flammable fibers are thought to aid in retaining the char formed when the composite is subjected to flame, to protect the composite under the charred surface.
  • the nonflammable fibers can be selected from such fibers as carbon fibers, ceramic fibers, and aramide fibers, with ceramic fibers being preferred.
  • the fibers should be fine fibers with average diameters of less than 5 micrometres and lengths of less than 100 millimetres so that the fibers can be evenly and easily distributed throughout the mixture.
  • the carbon black added can be any of the usual sulfur-free carbon blacks used as additives in silicone elastomers cured with a platinum catalyst. The carbon black is sulfur-free because sulfur might interfere with the cure.
  • the flame retardant additive filler comprises an intumescent flame retardant.
  • the intumescent flame retardant comprises expandable graphite (EG) particles.
  • the expandable graphite particles have a diameter ranging from 200 to 708300 ⁇ m, from 2000 to 70830 ⁇ m, from 2000 to 7083 ⁇ m, and/or are in amount of from 5 to 12%by weight, from 6 to 11%by weight, from 7 to 10%by weight, from 8 to 9%by weight, based on the total weight of the halogen free flame-retardant silicone composition.
  • EG is a low-density carbon material having a series of unique properties: developed specific surface, binder-free pressing capacity, stability to aggressive media, and low thermal conductivity.
  • the structure of graphite consists of layers in which there are coupled six-membered aromatic cyclic systems. Carbon atoms within a graphite layer are covalently bonded, while layers are bound by weak van der Waals forces.
  • EG acts as a blowing agent as well as a carbonization agent. As shown in Figure 3, heating of the treated graphite results in the conversion of the intercalant from a solid phase to a gas phase.
  • the expandable graphite particles can be treated or stabilized with an intercalant material, selected from the group consisting of intercalation compounds of SOx and NOx, where x is selected from an integer from 1 to 3.
  • expandable graphite particles may include, for example, expandable graphite particles stabilized with acids such as nitric acid, sulfuric acid, and their mixtures.
  • component (E) can be selected from the group consisting of platinum, palladium, rhodium, nickel, iridium, ruthenium catalysts and mixtures thereof, preferably platinum catalyst, which can efficiently promote the reaction of -SiH groups with vinyl groups.
  • platinum catalyst which can efficiently promote the reaction of -SiH groups with vinyl groups.
  • Particularly preferred is a two-part halogen free flame-retardant silicone composition wherein the catalyst is an organoplatinum compound.
  • a two-part halogen free flame-retardant silicone composition wherein the catalyst is functional organoplatinum compound selected from an ( ⁇ -diolefin) ( ⁇ -aryl) platinum complex, an ( ⁇ -diolefin) ( ⁇ -aryl) -platinum complex, an ( ⁇ -diolefin) ( ⁇ -alkyl) -platinum complex, and mixtures thereof. It is possible to use commercially available products in the present invention.
  • component (E) may be incorporated into the halogen free flame-retardant silicone composition in an amount of from 0.10%to 2.0%by weight, from 0.50%to 1.5 %by weight or from 0.80%to 1.3%by weight, such as 1.2 %by weight, based on the total amount of the halogen free flame-retardant silicone composition.
  • the hydrosilylation catalyst inhibitor is an optional component, which can slow the reaction rate by inhibiting the hydrosilylation catalyst as needed so that mixing can be completed before the mixture starts curing reaction. Therefore, it shall be understood that in case curing cannot be conducted quickly during and right after mixing, it may become necessary to add hydrosilylation catalyst inhibitor, but in case curing can be conducted immediately right after mixing, it may not need to add hydrosilylation catalyst inhibitor. Determining whether it needs to add hydrosilylation catalyst inhibitor into the polysiloxane composite is within the capability of one of ordinary skill in the art.
  • hydrosilylation catalyst inhibitor examples comprise methylvinylcyclosiloxane, tetravinyltetramethyl- cyclotetrasiloxane (vinyl D4) , ethynylcyclohexanol (ECH) and mixtures thereof.
  • the hydrosilylation catalyst inhibitor may be incorporated into the halogen free flame-retardant silicone composition in an amount of from 0%to 2%by weight, from 0.05 %to 1.5 %by weight or from 0.5 %to 1.2 %by weight, such as 0.1 %by weight, based on the total amount of the halogen free flame-retardant silicone composition, which depends on desired curing speed.
  • thalogen free flame-retardant silicone composition can optionally comprise a pigment, which is selected from the group consisting of carbon black, titanium oxide, iron oxide red, and combinations thereof.
  • the pigment may be incorporated into the halogen free flame-retardant silicone composition in an amount of from 0%to 2%by weight, from 0.05 %to 1.5 %by weight or from 0.5 %to 1.2 %by weight, such as 0.2 %by weight, based on the total amount of the halogen free flame-retardant silicone composition.
  • the halogen free flame-retardant silicone composition can optionally comprise an insulant filler, which generlly has an electrical insulation value, i.e. a dielectric strength, of greater than about 10 kV/mm.
  • an insulant filler comprises metal oxides, metal nitrides, metal carbides, metal hydroxides, metal carbonates, metal sulfates, natural and synthetic minerals mainly silicates, and aluminum silicates; and mixtures thereof.
  • insulant filler useful in the present invention may include quartz, fused silica, natural silica, synthetic silica, natural aluminum oxide, synthetic aluminum oxide, slate, hollow fillers, aluminum trihydroxide, magnesium hydroxide, aluminum hydroxide oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, mica, zinc oxide, aluminum nitride, mullite, wollastonite, vermiculite, talcum, glimmer, kaolin, bentonite, xonolit, andalusite, zeolithe, dolomite, glass powder, glass fibers, glass fabrics, other organic or inorganic particulate fillers, and mixtures thereof.
  • the insulant filler used in the present invention may be selected from the group consisting of quartz, natural silica, synthetic silica, natural aluminum oxide, synthetic aluminum oxide, boron nitride, aluminum nitride, wollastonite, glass powder, glass fibers, and glass fabrics.
  • the insulant filler may be incorporated into the halogen free flame-retardant silicone composition in an amount of from 0%to 1%by weight, from 0.1 %to 0.8 %by weight or from 0.15 %to 0.5 %by weight, such as 0.25 %by weight, based on the total amount of the halogen free flame-retardant silicone composition.
  • halogen free flame-retardant silicone composition was produced as follows:
  • Component A1 and component E were mixed using a Speed mixer in a container, to form Part A.
  • Component A1 and component A2, as well as optinoal pigments were mixed using a Speed mixer in a container, to form Part B.
  • Component B, component C and component D, as well as optional insulant filler are introduced gradually into Part A or Part B under room temperature (RT) , and then mixed Part A and Part B to form a halogen free flame-retardant silicone composition in form of paste.
  • RT room temperature
  • the latent heat storage material and flame-retardant pottant can be made by curing the halogen free flame-retardant silicone composition.
  • polymers and gelling agents were mixed homogeneously, which did not contain PCM (s) , FR fillers and catalysts, by using FLECKTech mixer in 500rpm, 1500rpm and 3000rpm step by step. Part A and part B were obtained. Before use, each base formulations needs to be mixed again. In part A, a catalyst was added just before use.
  • Inorganic thermal conductive filler, FR Fillers and PCM (s) were added according to the formulation requirements. After mixing by using FLECKTech mixer in 500rpm, 1500rpm and 3000rpm step by step, viscosity and thermal conductivity are tested.
  • Shore hardness A was measured according to ASTM C661-15.
  • Specimen were tested according to the UL-94 vertical burning test method in CZF-2 Vertical Burning Tester made by Nanjing Jiangning Analytical Equipment Company. Each composite was tested at least 5 times repeatedly. Three kinds of standard thickness, 0.3mm on PCB substrate, 0.5mm on PCB substrate and 3.00mm free standing samples were used for fire resistance testing, with after flame time t1 and t2 recorded. The conditions is more strict with thickness increasing. Chamber was opened with air flow around the testing device.
  • Dielectric strength was measured with 6517B Electrometer/High Resistance Meter from Keithley Instrument, Inc, according to ASTM D257-07. The voltage rising rate is 1kV/sec.
  • Thermal conductivity was measured by Hotdisk transient technology with sensor C5501, heat time and power of 20s and 30mW.
  • Grease material was filled into two cups and put the planar sensor inside. Use fine-tuned analysis with temperature drift compensation and time correction selected between points 50-150.
  • the latent heat was measured with DSC (Differential Scanning Calorimetry) and carried out using Thermal analyzer at heating rates of 5 °C/min with a temperature range of 0 °C to 60 °C under a constant stream of nitrogen at atmospheric pressure.
  • IE 1 and IE2 represent full formulations with latent heat around 60-62J/g. Under different FR testing standard conditions on PCB substrate and free standing, by adjusting EG-A300 dosage from 6%to 10%, Inventive Examples reached to UL94V0 level. By increasing requirements of latent catalyst from around 60J/g to 100J/g, IE 3 and 4 also reached to UL94V0.
  • Figure 1 showed a Microtek TEM image of the halogen free flame-retardant silicone composition. Because expanded graphite is a conductive filler and high voltage will cause danger when charging, so insulant filler, crystal silica 708, was added when EG dosage was high. Under the insulant filler reached to 2.5%wt., the dielectric strength was decrease under 10KV/mm.
  • Table 3 showed all the test results and detailed formulations of Inventive examples. Compared with Comparative Examples in Table 4, the inorganic thermal conductive filler (e.g., APP and ATH) and flame-retardant additive filler (e.g., EG) were feasible to achieve UL94 V0.
  • the inorganic thermal conductive filler e.g., APP and ATH
  • flame-retardant additive filler e.g., EG
  • EG particle size can range from 100 to 300 ⁇ m.
  • 10%wt of EG-300A 300 ⁇ m passed 3.0mm free standing UV94 V0 test
  • 10%wt. of EG filler passed 1.5mm free standing UV94 V0 test. Larger particle size of EG had higher efficiency with better FR performance.

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Abstract

L'invention concerne une composition de silicone ignifuge exempte d'halogène, un matériau de stockage de chaleur latente et un agent d'enrobage ignifuge. La composition de silicone ignifuge exempte d'halogène comprend (A1) un siloxane contenant un alcényle, (A2) un intermédiaire siloxane contenant du Si-H ; (B) au moins une particule encapsulée changeant de phase ; (C) au moins une charge thermoconductrice inorganique ; (D) au moins une charge additive ignifuge ; et (E) un catalyseur de réaction d'hydrosilylation. Le matériau de stockage de chaleur latente et l'agent d'enrobage ignifuge présentent des propriétés ignifuges et des propriétés de stockage de chaleur latentes améliorées.
PCT/CN2023/111718 2023-08-08 2023-08-08 Compositions de silicone ignifuges exemptes d'halogène, matériau de stockage de chaleur latente et agent d'enrobage ignifuge Pending WO2025030366A1 (fr)

Priority Applications (2)

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PCT/CN2023/111718 WO2025030366A1 (fr) 2023-08-08 2023-08-08 Compositions de silicone ignifuges exemptes d'halogène, matériau de stockage de chaleur latente et agent d'enrobage ignifuge
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