WO2017012119A1 - Particules à structure cœur-coque thermoconductrices - Google Patents

Particules à structure cœur-coque thermoconductrices Download PDF

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WO2017012119A1
WO2017012119A1 PCT/CN2015/084938 CN2015084938W WO2017012119A1 WO 2017012119 A1 WO2017012119 A1 WO 2017012119A1 CN 2015084938 W CN2015084938 W CN 2015084938W WO 2017012119 A1 WO2017012119 A1 WO 2017012119A1
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particle
hexagonal boron
boron nitride
polymer
composite material
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PCT/CN2015/084938
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Yan Huang
Hongyu Chen
Yunfeng Yang
Libo DU
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Dow Global Technologies Llc
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    • H05K1/02—Details
    • H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
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    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
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Definitions

  • the present invention relates to thermally conductive particles with core-shell structure, a method for forming the particles, a composition comprising the particles and a resin and a polymer composite material formed from the composition, which is useful for a thermal management element of electronic devices.
  • Thermal management is critical in every aspect of the microelectronics space, such as integrated circuits (IC) , light-emitting diode (LED) , power electronics, displays and photovoltaics.
  • IC integrated circuits
  • LED light-emitting diode
  • the performance of these devices can be directly affected by operating temperature. Lowering the operating temperature of these devices often increases lifetime and improves performance, as compared to operation at higher temperatures.
  • thermally conductive fillers are added in polymer materials.
  • Hexagonal boron nitride is thought to be an excellent thermally conductive filler because of its high thermal conductivity, low electrical conductivity and no hydrolysis properties.
  • polymer materials comprising hexagonal boron nitride fillers often show anisotropic thermal conductivity (i.e.
  • agglomerated hexagonal boron nitride or a mixture of hexagonal boron nitride and other thermally conductive filler was used in a polymer materials, see e.g. US6, 794, 435B, US6, 764, 975B, US6, 645, 612B, US5, 898, 009A, US8, 394, 489A, US5, 854, 155A, JP04906243B, US2012-0046387A, CN101318636B, JP2008-001536A and US2006-0127422A.
  • many additional steps are needed to prepare agglomerated hexagonal boron nitride.
  • thermally conductive fillers are increased and cause difficulty of processability because of increased viscosity. Therefore, isotropic thermally conductive filler both for thorough-plane direction and in-plane direction and a polymer material with easy processability and high thermal conductivity suitable for a thermal management element of electronic devices is desired.
  • the present inventors have now found a technical approach to get isotropic thermal conductivity using hexagonal boron nitride and another ceramic particle by a use of a complex particle having a center part formed by a ceramic particle and a layer on the surface of the center part formed by hexagonal boron nitride and a polymer.
  • the center part is called core
  • the layer on the surface of the center part is called shell.
  • the core-shell structured particle has almost spherical morphology comes from a figure of ceramic particle, and hexagonal boron nitrides are layered in all different directions. Therefore, a polymer material comprising the core-shell structured particle has isotropic thermal conductivity which is useful for thermal management elements of electronic devices.
  • one aspect of the invention relates to a particle having a core formed from a ceramic particle with 1 to 300 micro meters of diameter and covering at least part of the surface of the core a layer comprising hexagonal boron nitride and a polymer, wherein the length of the hexagonal boron nitrides is 0.9 times or less of the diameter of the core.
  • Another aspect of the invention relates to a method for forming the particle, comprising the steps of: (a) preparing a mixture comprising from 20 to 80 volume%of ceramic particles with 1 to 300 micro meters of diameter, from 10 to 60 volume%of hexagonal boron nitride and from 5 to 50 volume%of polymer, in which the length of the hexagonal boron nitrides is 0.9 times or less of the diameter of the ceramic particle, and (b) heating the mixture under mixing.
  • compositions comprising the particle and a resin, a polymer composite material formed from the composition, a shaped article formed from the polymer composite material and an electronic device comprising a thermal management component formed from the polymer composite material.
  • Fig. 1 is a SEM photograph for original hexagonal boron nitride, which is used in Inventive examples 1 to 3 and Comparative example 1.
  • Fig. 2 is a SEM photograph for original Al 2 O 3 , which is used in Inventive examples 1 to 3 and Comparative example 1.
  • Fig. 3 is a SEM photograph for Al 2 O 3 /epoxy/hexagonal boron nitride hybrid particles obtained in Inventive example 1 (magnification is 1,000 times) .
  • Fig. 4 is a SEM photograph for Al 2 O 3 /epoxy/hexagonal boron nitride hybrid particles obtained in Inventive example 1 (magnification is 2,000 times) .
  • Fig. 5 is a SEM photograph for cross-section of injection molded plaques obtained in Comparative example 1.
  • Fig. 6 is a SEM photograph for cross-section of injection molded plaques obtained in Inventive example 3.
  • the particle of the invention has a center part and a layer on the surface of the center part.
  • the center part is at least partially covered by the layer.
  • the center part is formed from a ceramic particle with 1 to 300 micro meters of diameter and the layer comprises hexagonal boron nitride and a polymer.
  • the center part is called as core, and the layer on the surface of the center part is called as shell. Therefore, the particle is also called as core-shell structured particle.
  • the ceramic particle used in the invention may be selected wide variety of ceramics.
  • ceramics include aluminum oxide (Al 2 O 3 ) , magnesium oxide (MgO) , silica oxide (SiO 2 ) and aluminum nitride (AlN) .
  • the ceramic is Al 2 O 3 .
  • the ceramic particle preferably is substantially spherical. In this patent application, substantially spherical shape means the ratio of the longest diameter of a particle to the shortest diameter of the particle is from 1 to 1 to 1 to 0.8. However there can be some irregularities on the surface.
  • the particle size of the ceramic is from 1 to 300 micro meters of diameter. At least 95%of particles are included in the range. Particle size of the ceramic can be analyzed by laser diffraction method.
  • the surface of the core is at least partially covered by a layer (shell) .
  • a layer Preferably, at least 80%of the surface of the core is covered by the shell, the most preferably, 90%of the surface is covered by the shell.
  • the shell comprises hexagonal boron nitride and a polymer.
  • hexagonal boron nitride has plate-like morphology.
  • the plate-like morphology of hexagonal boron nitride comes from its hexagonal crystal structure, i.e. a layer of sheets formed by boron atoms and nitrogen atoms.
  • the vertical direction against the plane of a plate-like morphology is short while the horizontal direction is long.
  • the vertical direction is called as thick, while the horizontal direction is called as length. Length means the longest distance of a plate-like morphology of hexagonal boron nitride.
  • the length of hexagonal boron nitride is 0.9 times or less of the diameter of the center part (core) .
  • a core-shell structured particle can be formed.
  • the length of hexagonal boron nitride is 0.7 times or less of the diameter of the core, most preferably the length is 0.5 times or less, further preferably, the length is 0.2 times or less of the diameter of the core.
  • the layer (shell) comprises a polymer.
  • the polymer works as a binder to attach hexagonal boron nitride onto the surface of a ceramic particle.
  • the polymer is preferably thermoset plastics.
  • examples of the polymer used in the invention include epoxy resins, phenolic resins, ureas, melamine resins, cross-linked polyesters, cross-linked silicones, rubbers, cyanate ester, bismaleimide, polyimide, cross-linked acrylate copolymers, and polyurethane resins.
  • the content of the hexagonal boron nitride in shell is preferably 70 wt%or more, more preferably 80 wt%or more based on the entire weight of the shell. At the same time, the content of the hexagonal boron nitride is preferably 97 wt%or less, more preferably 95 wt%or less based on the entire weight of the shell.
  • the thickness of the shell is preferably from 0.1 to 10 micrometers, more preferably from 0.2 to 5 micrometers.
  • the shell can comprise other ingredients such as antioxidant, UV stabilizer or flame retardant agent. But preferably, the shell is formed by hexagonal boron nitride and a polymer.
  • the first step of the method is preparing a mixture comprising ceramic particles, hexagonal boron nitride and polymer in which the sizes of the ceramic particles are from 1 to 300 micrometers of diameter and the length of the hexagonal boron nitrides is 0.9 times or less of the diameter of the ceramic particle.
  • the polymer is preferably thermoset plastics.
  • the mixture may comprise a curing agent and a catalyst to help the cure of the thermoset plastics.
  • the contents of each element are, from 20 to 80 volume%for ceramic particles, from 10 to 60 volume%for hexagonal boron nitride and from 5 to 50 volume%for polymer, based on the volume of the mixture.
  • the mixture comprises a curing agent and/or a catalyst, the contents of those are 30 to 60 wt%and 0.1 to 0.8 wt%respectively based on the total weight of polymer.
  • the mixture is heated to the temperature of curing temperature of the polymer under mixing.
  • the mixing of the mixture can be conducted by any known methods, such as speed mixer or mixing roller.
  • the mixing speed is 2,000 rpm or more.
  • the temperature may be increased step by step.
  • core-shell structured particles are obtained.
  • core-shell structured particles can be screened using a sieve. The core-shell structured particles are confirmed by SEM observation and increased sizes of the particles.
  • the obtained core-shell structured particles have many good properties.
  • the core-shell structured particles have almost spherical shapes. Therefore, the flowability of the particles in a resin composition during molding of the composition is higher than the flowability of the hexagonal boron nitride itself. The increased flowability affects better processability of a polymer composite material formed from the resin composition.
  • the surface of the particle is covered by shell comprising hexagonal boron nitride, and the hexagonal boron nitride in the shell are layered in random directions. Therefore, the core-shell structured particles of this invention have isotropic thermal conductivity.
  • the core-shell structured particle has a shell comprising hexagonal boron nitride and a polymer, so the surface of the particle is softer than the surface of a ceramic particle. Therefore, the core-shell structured particles reduce tool wearing issue, i.e. the structure prevents scratches of an instrument by hard ceramics particle.
  • the composition of the invention comprises the particle and a resin.
  • Any resin can be used for the composition.
  • the resin can be thermoplastic resins, thermosetting resins, or mixture thereof.
  • the resin include polyamide (PA) , nylons, polyphenylene sulfide (PPS) , polyolefin, polyacetal, polycarbonate (PC) , polystyrene (PS) , polyester, liquid crystal polyester (LCP) , polyethylene telephthalate (PET) , acrylonitrile-butadiene-stylene (ABS) , polytetrafluoroethylene (PTFE) , polyvinyl fluoride (PVF) , polyoxymethylene (POM) , polybutadiene terephthalate (PBT) , polyphenylene oxide (PPO) , polyetheretherketone (PEEK) , polyetherimide (PEI) and polymethyl methacrylate (PMMA) .
  • PA polyamide
  • PPS polyphen
  • the content of the particles in the composition is preferably 15 volume%or more, more preferably 30 volume%or more based on the entire volume of the composition. At the same time, the content of the particles in the composition is preferably 80 volume%or less, more preferably 70 volume%or less.
  • composition used in the invention can comprise other additives such as flame retardant, antioxidant, UV stabilizer, plasticizer, coupling agent, mold release agent, pigment and dye.
  • additives such as flame retardant, antioxidant, UV stabilizer, plasticizer, coupling agent, mold release agent, pigment and dye.
  • Those additives can be added to at least one of sea phase or island phase.
  • flame retardant used for the composition examples include antimony oxides, halocarbon, halogenated ester, halogenated ether, brominated flame retardant agent, and halogen free compounds such as organophosphorus compounds, organonitrogen compounds, intumescent flame retardants.
  • antioxidant used for the composition examples include sodium sulfite, sodium pyrosulfite, sodium hydrogen sulfite, sodium thiosulfate and dibutyl phenol.
  • UV stabilizer used for the composition examples include benzophenones, benzotriazoles, substituted acrylates, aryl esters and compounds containing nickel or cobalt salts.
  • plasticizer used for the composition examples include phthalates benzoates, dibenzoates, thermoplastic polyurethane plasticizers, phthalate esters, naphthalene sulfonate, trimellitates, adipates, sebacates, maleates, sulfonamides, organophosphates, polybutene.
  • Examples of coupling agent used for the composition include chrome complex, silane coupling agent, titanate coupling agent, zirconium coupling agent, magnesium coupling agent and tin coupling agent.
  • mold release agent used for the composition examples include inorganic mold release agent such as talcum powder, mica powder, argil and clay; organic mold release agent such as aliphatic acid soap, fatty acid, paraffin, glycerol and vaseline; polymer mold release agent such as silicone oil, polyethylene glycol and polyethylene.
  • pigment or dye used for the composition of the invention examples include chromate, sulfate, silicate, borate, molybdate, phosphate, vanadate, cyanate, sulfide, azo pigment, phthalocyanine pigment, anthraquinone, indigo, quinacridone and dioxazinedyes.
  • the polymer composite material of the invention can be formed from the composition disclosed above.
  • the polymer composite material is obtained by blending, extruding, pouring, etc. the matrix resin with the particles. To form an article the material is shaped, e.g. by molding, extruding, coating, etc. and then cooled. If the matrix resin includes a thermosetting resin, a curing step is further added to the above process.
  • the polymer composite material of the invention has isotropic thermal conductivity for different directions.
  • the isotropic thermal conductivity means the ratio of through plane and in-plane thermal conductivity (through plane thermal conductivity /in-plane thermal conductivity) is larger than 0.5.
  • the in-plane thermal conductivity of the polymer composite material is preferably 4 W/m ⁇ K or more, and the through-plane thermal conductivity of the polymer composite material is preferably 2 W/m ⁇ K or more.
  • the polymer composite material of the invention can be used for thermal management components of electronic devices.
  • electronic devices comprise integrated circuit (IC) chip, light-emitting diode (LED) , power electronics, displays and photovoltaics.
  • IC integrated circuit
  • LED light-emitting diode
  • power electronics displays and photovoltaics.
  • the polymer composite material can be used as a heat sink or connecting material with heat source and heat sink.
  • Heat sink is used to cool electronics components or semiconductor components such as high-power semiconductor devices, and optoelectronic devices such as higher-power lasers and light emitting diodes (LEDs) . Since the polymer composite material of our invention has isotropic thermal conductivity, the heat generated by the heat source is effectively transferred and removed from the heat source.
  • thermal management components are, electronic packaging material, sealing material, adhesive material, electric switch, printed circuit board and wire coating.
  • the polymer composite material of the invention can be used for a substrate with electronics element or semiconductor element such as IC chips or power electronics (heat source) and plastic substrate or plastic film contacted to such heat source (a thermal management component) .
  • IC chips or other electronics elements are normally mounted on a laminated plastic substrate such as epoxy or polyimide resin.
  • Ceramic substrate such as aluminum or aluminum nitrate is also used as a substrate for power electronics because of the need for heat management generated by the power electronics. Since ceramic substrate is difficult to laminate or process, plastic substrate with high thermal conductivity is desired.
  • the polymer composite material of our invention can be used for the purpose.
  • the polymer composite material of the invention can be used for a system comprising electronics device (heat source) and a covering thermosetting resin of the device (a thermal management component) .
  • electronics device heat source
  • thermosetting resin thermosetting resin
  • thermal management of the material is required.
  • the polymer composite material of our invention with isotrophic thermal conductivity can be used for the purpose.
  • Example of such article is LED lightning system with LED light encapsulated by the cured thermosetting resin.
  • the polymer composite material of the invention can be used for a solid state lightening system comprising LED light (heat source) and a base which is mounted the LED light (a thermal management component) .
  • LED light heat source
  • a base which is mounted the LED light (a thermal management component)
  • thermal management component a component that is required.
  • the polymer composite material of our invention with isotrophic thermal conductivity can be used for the purpose.
  • MTHPA methyl tetrahydrophothalic anhydride
  • BDMA benzyldimethylamine
  • the weight ratio of DER331/MTHPA/BDMA was 100/90/0.5.
  • the epoxy in the mixture was fully cured via heating at 90 °C for 2h, 100 °C for 2h; 120 °C for 2h; 140 °C for 4h, 160 °C for 4h.
  • the volume ratio of Al 2 O 3 /epoxy/hexagonal boron nitride hybrid particle is fixed at 45/10/45.
  • Figures 1 to 4 show SEM images of original hexagonal boron nitride, original Al 2 O 3 and the prepared Al 2 O 3 /epoxy/hexagonal boron nitride hybrid particles.
  • hexagonal boron nitride with platelet shape was attached to the surface of spherical Al 2 O 3 by the cured epoxy.
  • the hybrid particles still show spherical morphology.
  • the samples (thin plaque) for TC measurement and morphology observation were prepared by injection molding (Machine: Fanuc ⁇ 28 mm, Clamp Tonnage: 200. ) : Conditions are listed in the Table 1. Size of the thin plate mold was 1mm*60mm*60mm. The thickness of injection plaques was 1 mm.
  • the thermal diffusivity ⁇ (mm 2 /s) was determined with Netzsch Nanoflash LFA 447 instrument according to ASTM D1461-01. The measurement temperature was 25 °C.
  • the samples for TC measurement were cut from the injection molded plaques. Diameter 11.8-12.6 mm, thickness ⁇ 1.0 mm for through-plane TC measurement and diameter 24.8-25.4 mm, thickness ⁇ 0.5 mm for in-plane TC measurement.
  • a laser light absorbing spray was applied to surfaces of disk-shaped samples, and then the samples were dried in air. Four laser flash shots were conducted and then the average ⁇ and standard deviation was obtained.
  • the density ⁇ (g/cm 3 ) of the samples at room temperature was measured by hydrostatic weighing, in which the displacement of water due to a submerged object was used to determine the density of the object.
  • the heat capacity Cp (J/g C) at 25 °C of the samples was determined by DSC (DSC-Q2000) according to ASTM E1269-11.
  • Injection molded plaques were cut into pieces for cross-section imaging. Pieces were embedded in epoxy and metallurgically polished prior to imaging. Polished pieces were observed by back scattering electron detector using Nova Nano630 SEM.
  • Figures 5 and 6 show SEM images of cross-section of injection molded plaques of Comparative example 1 and Inyentive example 3 respectively.
  • the hexagoral boron nitride are mostly free and oriented in the flow direction of injection molding in spite of the Al 2 O 3 interrupt.
  • less hexagonal boron nitride oriented in the flow direction, and many hexagonal boron nitride are surrounding the spherical Al 2 O 3 to different directions, which was bound by epoxy. This is responsible for the increase of through-plane TC.
  • the plate-like boron nitride (hexagonal boron nitride) was successfully attached to the surface of spherical Al 2 O 3 to form a core/shell structured Al 2 O 3 /epoxy/hexagonal boron nitride hybrid particle.
  • the hexagonal boron nitride is randomly distributed and fixed on the surface of Al 2 O 3 , and the use of the hybrid particles to replace part of original hexagonal boron nitrie and Al 2 O 3 can increase the through-plane TC of composites.

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  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne des particules à structure cœur-coque thermoconductrices, un procédé de formation desdites particules, une composition les contenant et une résine et un matériau composite polymère formés à partir de ladite composition. La particule est utile pour un élément de gestion thermique de dispositifs électroniques.
PCT/CN2015/084938 2015-07-23 2015-07-23 Particules à structure cœur-coque thermoconductrices WO2017012119A1 (fr)

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EP3797863A1 (fr) * 2019-09-27 2021-03-31 SHPP Global Technologies B.V. Poudres de particules c ur-écorce de polymère-céramique et procédés de fabrication et articles comprenant ces poudres
EP3797862A1 (fr) * 2019-09-27 2021-03-31 SHPP Global Technologies B.V. Poudres de particules c ur-écorce semi-cristallines de polymère-céramique et procédés de fabrication et articles comprenant ces poudres
EP3816218A1 (fr) * 2019-10-30 2021-05-05 Hamilton Sundstrand Corporation Composite de céramique polymère et leurs procédés de fabrication
TWI734552B (zh) * 2019-07-11 2021-07-21 日商昭和電工股份有限公司 被覆二氧化矽的氮化硼粒子之製造方法、散熱性樹脂組成物之製造方法
CN114456776A (zh) * 2022-01-27 2022-05-10 湖南创瑾技术研究院有限公司 一种导热填料及其制备方法与应用
JP7308426B1 (ja) 2022-01-24 2023-07-14 長野県 窒化ホウ素被覆熱伝導性粒子及びその製造方法並びに熱伝導樹脂組成物及び熱伝導性成形体
CN116462971A (zh) * 2023-04-24 2023-07-21 宁波能之光新材料科技股份有限公司 一种锂电池用导热绝缘硅凝胶复合材料的制备方法
CN116715938A (zh) * 2023-08-07 2023-09-08 四川大学 基于介电泳力取向的环氧树脂复合绝缘材料及其制备方法

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KR20200080961A (ko) 2018-12-27 2020-07-07 마이크로컴퍼지트 주식회사 절연 방열 나노와이어, 이의 제조방법 및 이를 포함하는 복합체
CN110218390A (zh) * 2019-06-13 2019-09-10 合肥工业大学 一种具有核壳结构导热填料填充的聚丙烯复合材料
TWI734552B (zh) * 2019-07-11 2021-07-21 日商昭和電工股份有限公司 被覆二氧化矽的氮化硼粒子之製造方法、散熱性樹脂組成物之製造方法
EP3797863A1 (fr) * 2019-09-27 2021-03-31 SHPP Global Technologies B.V. Poudres de particules c ur-écorce de polymère-céramique et procédés de fabrication et articles comprenant ces poudres
EP3797862A1 (fr) * 2019-09-27 2021-03-31 SHPP Global Technologies B.V. Poudres de particules c ur-écorce semi-cristallines de polymère-céramique et procédés de fabrication et articles comprenant ces poudres
WO2021059217A1 (fr) * 2019-09-27 2021-04-01 Shpp Global Technologies B.V. Poudres de particules cœur-écorce en céramique polymère, et procédés de fabrication et articles comprenant de telles poudres
WO2021059218A3 (fr) * 2019-09-27 2021-05-27 Shpp Global Technologies B.V. Poudres de particules cœur-écorce en céramique-polymère semi-cristallin, et processus de fabrication et articles comprenant de telles poudres
CN114728253A (zh) * 2019-09-27 2022-07-08 高新特殊工程塑料全球技术有限公司 半结晶聚合物-陶瓷核-壳颗粒粉末及其制备方法和包含该粉末的制品
CN114746171A (zh) * 2019-09-27 2022-07-12 高新特殊工程塑料全球技术有限公司 聚合物-陶瓷核-壳颗粒粉末及其制备方法和包含该粉末的制品
EP3816218A1 (fr) * 2019-10-30 2021-05-05 Hamilton Sundstrand Corporation Composite de céramique polymère et leurs procédés de fabrication
JP2023107431A (ja) * 2022-01-24 2023-08-03 長野県 窒化ホウ素被覆熱伝導性粒子及びその製造方法並びに熱伝導樹脂組成物及び熱伝導性成形体
JP7308426B1 (ja) 2022-01-24 2023-07-14 長野県 窒化ホウ素被覆熱伝導性粒子及びその製造方法並びに熱伝導樹脂組成物及び熱伝導性成形体
CN114456776A (zh) * 2022-01-27 2022-05-10 湖南创瑾技术研究院有限公司 一种导热填料及其制备方法与应用
CN114456776B (zh) * 2022-01-27 2024-03-15 湖南创瑾技术研究院有限公司 一种导热填料及其制备方法与应用
CN116462971A (zh) * 2023-04-24 2023-07-21 宁波能之光新材料科技股份有限公司 一种锂电池用导热绝缘硅凝胶复合材料的制备方法
CN116715938A (zh) * 2023-08-07 2023-09-08 四川大学 基于介电泳力取向的环氧树脂复合绝缘材料及其制备方法
CN116715938B (zh) * 2023-08-07 2023-10-13 四川大学 基于介电泳力取向的环氧树脂复合绝缘材料及其制备方法

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