WO2016086587A1 - Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof - Google Patents

Thermally conductive and insulating epoxy resin composition and preparation method therefor and use thereof Download PDF

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WO2016086587A1
WO2016086587A1 PCT/CN2015/078193 CN2015078193W WO2016086587A1 WO 2016086587 A1 WO2016086587 A1 WO 2016086587A1 CN 2015078193 W CN2015078193 W CN 2015078193W WO 2016086587 A1 WO2016086587 A1 WO 2016086587A1
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epoxy resin
component
resin composition
mixture
accounts
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PCT/CN2015/078193
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French (fr)
Chinese (zh)
Inventor
王好盛
张冬海
薛杨
陈赟
邬瑞文
张婧坤
陈运法
高锋
陈卓
张晖
张忠
尹立
张翀
�田�浩
袁端鹏
郝留成
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中国科学院过程工程研究所
国家纳米科学中心
国网智能电网研究院
平高集团有限公司
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Publication of WO2016086587A1 publication Critical patent/WO2016086587A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • 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
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the invention belongs to the field of materials, and in particular, to a thermally conductive and insulating epoxy resin composition, a preparation method and use thereof.
  • thermal interface materials used in high voltage electrical appliances such as switchgear, transformers, rotating electrical machines, GIS, and high density integrated insulated electronic devices such as packaging systems require not only excellent dielectric properties, mechanical properties, but also high thermal conductivity.
  • Epoxy resins can be widely used in the above-mentioned electrically insulating materials, but their thermal conductivity is only 0.2 W/m ⁇ K.
  • the main method to improve the thermal conductivity of epoxy resin is to introduce high thermal conductive insulating filler into the epoxy resin to prepare the filled composite material to obtain improved thermal conductivity, and to ensure the dielectric properties of the material.
  • the epoxy resin composition provided by the invention has high thermal conductivity, and excellent electrical properties such as breakdown strength.
  • a high thermal conductive insulating epoxy resin composition comprising the following components:
  • the component (C) accounts for 50% to 70% by mass of the epoxy resin composition, for example, 53%, 58%, 64%, 69%, etc.;
  • the component (D) accounts for 15% to 35% by mass of the epoxy resin composition, for example, 17%, 23%, 28%, 33%, and the like.
  • the component (C) boron nitride agglomerate of the present invention has a large particle size and isotropic, and the thermal conductivity of the system can be greatly improved as compared with the flaky boron nitride.
  • the component (D) comprises two particles of different sizes, respectively:
  • component (D) of the invention enables the particle size and morphology to be compounded with each other, improves the filling rate of the particles, can improve the electrical properties such as the breakdown strength of the system, and can further improve the thermal conductivity of the system.
  • the component (A) is a bisphenol A epoxy resin, a bisphenol F epoxy resin, an alicyclic epoxy resin, a novolac epoxy resin or a polyfunctional glycidyl ether ring.
  • the component (A) accounts for 10 to 25% by mass of the epoxy resin composition, for example, 12%, 15%, 18%, 23%, and the like.
  • the component (B) is one or a mixture of two or more of an aromatic acid anhydride, an alicyclic acid anhydride, a polyfunctional acid anhydride, or a linear aliphatic acid anhydride.
  • the component (B) accounts for 5 to 10% by mass of the epoxy resin composition, for example, 7%, 8.5%, 9.4%, 9.9%, and the like.
  • the component (C) has a D50 particle diameter of 30 to 90 ⁇ m, preferably 30 to 70 ⁇ m.
  • the component (C) accounts for 55 to 65% by mass of the epoxy resin composition.
  • the preparation route of the boron nitride agglomerate used in the present invention is as follows: 500 g of hexagonal boron nitride having a D50 particle diameter of 0.5-4 ⁇ m, 10 g of surfactant KH560, and 450 g of deionized water are stirred at high speed to form a uniform slurry, and hydroxide is added.
  • the ammonium buffer adjustment system had a pH of 7.8, and 25 g of a binder polyvinyl alcohol was added thereto, followed by spray drying to obtain a boron nitride agglomerate.
  • the obtained boron nitride agglomerates were sintered at a high temperature of 1850 ° C under argon atmosphere, and then decarburized at 500 ° C under air to obtain a final boron nitride agglomerate having a D50 particle size of 30-90 ⁇ m.
  • the component (D) accounts for 20 to 30% by mass of the epoxy resin composition.
  • (a) accounts for 1 to 10% by mass of the component (D), and (b) of the component (D) accounts for the component (D).
  • the mass percentage is 90 to 99%.
  • the (a) nano inorganic particles in the component (D) have a D 50 particle diameter of 30 to 50 nm.
  • the (a) nano inorganic particles in the component (D) are spherical particles having a sphericity of ⁇ 0.85, preferably ⁇ 0.9, further preferably ⁇ 0.95.
  • the (b) micron inorganic particles in the component (D) have a D 50 particle diameter of 5 to 10 ⁇ m.
  • the nano inorganic particles in the component (D) and the (b) micro inorganic particles in the component (D) are each independently selected from the group consisting of inorganic oxides and nitrides. Or any one or a mixture of two or more of silicate compounds.
  • the nitride may be selected from any one or a mixture of two or more of boron nitride (BN), aluminum nitride (AlN) or silicon nitride (Si 3 N 4 ), preferably boron nitride. (BN).
  • BN boron nitride
  • AlN aluminum nitride
  • Si 3 N 4 silicon nitride
  • the inorganic oxide may be any one of alumina (Al 2 O 3 ), silicon oxide (SiO 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ) or titanium oxide (TiO 2 ). kind or a mixture of two or more.
  • the silicate compound may be selected from any one or a mixture of two or more of montmorillonite, vermiculite or mica.
  • the nano inorganic particles in the component (D) and the (b) micro inorganic particles in the component (D) are each independently BN.
  • the component (C) and the component (D) are each independently subjected to surface treatment.
  • the surface treatment agent used for the surface treatment is an organosilane coupling agent.
  • the organosilane coupling agent is a compound in which an organic group such as an amino group or an epoxy group and a hydrolyzable group such as an alkoxy group or an acyloxy group are bonded to a silicon atom.
  • the silane coupling agent is an organosilane coupling agent whose organic group is an epoxy group, preferably ⁇ -glycidoxypropyltrimethoxysilane or/and ⁇ -glycidoxypropane Triethoxy silane.
  • Another object of the present invention is to provide a method for preparing a thermally conductive and insulating epoxy resin composition according to the present invention, comprising the steps of:
  • the speed of the mixer during mixing in the step (1) is 500-1000 r/min.
  • the solvent in the step (2) is any one of acetone, methyl ethyl ketone, pentanone, xylene, dimethylformamide, methoxyethanol or a mixture of two or more, preferably Butanone.
  • the pressure of the solidification molding in the step (3) is 30-70 MPa
  • the curing molding process is two-stage curing.
  • the first stage curing temperature is 105-125 ° C, the time is 8-20 h; the second stage solidification temperature is 130-150 ° C, and the time is 7-16 h.
  • the present invention has the following beneficial effects: the insulating epoxy resin composition of the present invention has a high thermal conductivity of more than 13 W/m ⁇ K, a breakdown strength of 48 kV/mm or more, and a shape parameter of 18 or more. It can be used in high-voltage electrical appliances such as switchgear, transformers, rotating electrical machines, GIS and high-density integrated insulated electronic devices such as thermal interface materials in packaging systems.
  • test criteria for the properties of the thermally conductive and insulating epoxy resin composition of the present invention are as follows:
  • the test temperature is 23 ⁇ 2 ° C, 5 samples are tested, and the results are averaged.
  • the test was carried out according to the method specified in 5.1 of GB/T 1410-2006.
  • the test temperature was 23 ⁇ 2 ° C, and 8 samples were tested.
  • the Weibull distribution was used to calculate the breakdown strength E 0 and the shape parameter ⁇ .
  • the Weibull distribution is widely used to evaluate the statistical law of the breakdown behavior of insulating materials under alternating electric fields.
  • the expression of the two-parameter Weibull distribution is:
  • P(E) is the cumulative failure probability
  • E is the breakdown field strength of the sample
  • ⁇ is the shape factor characterizing the degree of data dispersion
  • the Weibull breakdown field strength is used to compare the electrical breakdown properties of different samples. The greater the concentration ⁇ of the material breakdown field strength distribution, the more stable the material's puncture resistance is.
  • the formulation amount of the component C boron nitride agglomerate, the component D (a) micron plate-shaped boron nitride, the component D (b) nano spherical boron nitride were uniformly mixed by a mixer to obtain a filler mixture.
  • the epoxy resin, the curing agent, the filler mixture and the solvent methyl ethyl ketone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring.
  • Oxygen composition The uncured epoxy composition was poured into a preheated mold and solidified at a pressure of 50 MPa. The curing conditions were cured at 115 ° C for 15 h and then cured at 140 ° C for 12 h.
  • the boron nitride agglomerate, the micron-plate boron nitride and the nano spherical boron nitride used in the embodiment 1-5 of the invention are all surface-treated, and the surface treatment agent is ⁇ -glycidoxypropyltrimethoxysilane. .
  • epoxy resin, curing agent, boron nitride agglomerate or micron-like boron nitride, solvent butanone are ultrasonically dispersed and uniformly mixed, and then further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT.
  • the solvent is removed under high temperature vacuum to form an uncured epoxy composition.
  • the uncured epoxy composition was poured into a preheated mold and solidified at a pressure of 50 MPa.
  • the curing conditions were cured at 115 ° C for 15 h and then cured at 140 ° C for 12 h.
  • the boron nitride aggregate and the micron-sized boron nitride used in Comparative Example 1-2 of the present invention are subjected to surface treatment, and the surface treatment agent is ⁇ -glycidoxypropyltrimethoxysilane.
  • Epoxy resin 100 100 Hardener 52 52 Boron nitride agglomerate 70 ⁇ m 650 Flake boron nitride 10 ⁇ m 650
  • micro-nano inorganic particle composition can improve the breakdown strength of the epoxy resin/boron nitride aggregate, and the increase of the shape parameter indicates that the puncture resistance is stable. At the same time, the thermal conductivity is kept stable, and the balance between thermal conductivity and insulation performance is achieved.
  • the component A of the formulation amount and the component D were uniformly mixed by a mixer to obtain a filler mixture.
  • the epoxy resin, the curing agent, the filler mixture, the solvent butanone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed disperser DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring.
  • Oxygen composition The uncured epoxy composition was poured into a preheated mold and solidified under a pressure of 30 MP. The curing conditions were cured at 105 ° C for 20 h and then cured at 130 ° C for 16 h.
  • Boron nitride aggregates, micron-plate boron nitride, micro-ellipsoids used in Embodiments 6-10 of the present invention The aluminum nitride, the nano-spherical alumina, and the nano-spherical silica are all surface-treated, and the surface treatment agent is ⁇ -glycidoxypropyltrimethoxysilane.
  • Comparative Example 1-2 Electrically Insulating Epoxy Resin Compositions Provided by the Invention are listed in Tables 5 and 6, respectively.
  • the formulation amount of the component C boron nitride agglomerate, the component D (a) micron plate-shaped boron nitride, the component D (b) nano spherical boron nitride were uniformly mixed by a mixer to obtain a filler mixture.
  • the epoxy resin, the curing agent, the filler mixture and the solvent methyl ethyl ketone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring.
  • Oxygen composition The uncured epoxy composition was poured into a preheated mold and solidified under a pressure of 70 MP. The curing conditions were cured at 125 ° C for 8 h and then cured at 150 ° C for 7 h.

Abstract

An insulating epoxy resin composition with a high thermal conductivity and a preparation method therefor. The composition comprises the following components: (A) one or more epoxy resins; (B) one or more anhydride curing agents; (C) a boron nitride aggregate; and (D) a micro-nano inorganic particle composition, wherein the mass percentage of the component (C) is 50%-70% of the epoxy resin composition; and the mass percentage of the component (D) is 15%-35% of the epoxy resin composition. The composition provided by the present invention has electric properties, such as a high thermal conductivity and an excellent breakdown strength.

Description

一种导热绝缘环氧树脂组合物、制备方法及其用途Thermal conductive insulating epoxy resin composition, preparation method and use thereof 技术领域Technical field
本发明属于材料领域，具体地，本发明涉及一种导热绝缘环氧树脂组合物、制备方法及其用途。The invention belongs to the field of materials, and in particular, to a thermally conductive and insulating epoxy resin composition, a preparation method and use thereof.
背景技术Background technique
随着电气、电子设备的大功率化和集成化，电流密度增加，热耗散和绝缘要求随之增加。因此用于高压电器如开关柜、变压器、旋转电机、GIS和高密度集成绝缘电子装置如封装系统中的热界面材料不仅需要优良介电性能、机械性能，而且需要高导热性。环氧树脂可以被广泛应用于上述电绝缘材料，但是其热导率只有0.2W/m·K。提高环氧树脂热导率的主要方法为在环氧树脂中引入高导热绝缘填料，制备填充型复合材料以获得提高的导热性能，同时需要保证材料的介电性能。With the increasing power and integration of electrical and electronic equipment, current density increases, and heat dissipation and insulation requirements increase. Therefore, thermal interface materials used in high voltage electrical appliances such as switchgear, transformers, rotating electrical machines, GIS, and high density integrated insulated electronic devices such as packaging systems require not only excellent dielectric properties, mechanical properties, but also high thermal conductivity. Epoxy resins can be widely used in the above-mentioned electrically insulating materials, but their thermal conductivity is only 0.2 W/m·K. The main method to improve the thermal conductivity of epoxy resin is to introduce high thermal conductive insulating filler into the epoxy resin to prepare the filled composite material to obtain improved thermal conductivity, and to ensure the dielectric properties of the material.
目前报道如CN 102532606，CN 103172913，CN 2011102516766中引入高热导填料如微米尺度氮化硼(BN)、氮化铝(AlN)等以增加热导率，但是所制备的环氧树脂复合材料的热导率通常也小于1W/m·K。US 7976941，US8404768报道采用大尺度聚集的氮化硼粉末可获得提高的热导率，但是此方法会严重降低环氧树脂的介电性能。上述已有技术均未见进一步提高环氧绝缘材料热导率同时保证体系介电性能的报道。It is currently reported that high thermal conductivity fillers such as micron-sized boron nitride (BN), aluminum nitride (AlN), etc. are introduced in CN 102532606, CN 103172913, CN 2011102516766 to increase thermal conductivity, but the heat of the prepared epoxy resin composite material. The conductivity is usually also less than 1 W/m·K. US 7,976,941, US Pat. No. 8,404,768 discloses the use of large-scale aggregated boron nitride powders to achieve improved thermal conductivity, but this method severely degrades the dielectric properties of epoxy resins. None of the above prior art reports have been found to further improve the thermal conductivity of the epoxy insulating material while ensuring the dielectric properties of the system.
发明内容Summary of the invention
为了克服现有技术的不足，本发明的目的之一在于提供一种导热绝缘环氧树脂组合物。本发明提供的环氧树脂组合物具有高导热性能，及优良的击穿强度等电气性能。 In order to overcome the deficiencies of the prior art, it is an object of the present invention to provide a thermally conductive and insulating epoxy resin composition. The epoxy resin composition provided by the invention has high thermal conductivity, and excellent electrical properties such as breakdown strength.
为达到上述的目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种高导热绝缘环氧树脂组合物，包括如下组分：A high thermal conductive insulating epoxy resin composition comprising the following components:
(A)一种或两种以上的环氧树脂；(A) one or two or more epoxy resins;
(B)一种或两种以上的酸酐固化剂；(B) one or two or more acid anhydride curing agents;
(C)氮化硼团聚体；(C) boron nitride agglomerates;
(D)微纳米无机颗粒组合物；(D) a micro-nano inorganic particle composition;
所述组份(C)占环氧树脂组合物的质量百分比为50％～70％，例如为53％、58％、64％、69％等；The component (C) accounts for 50% to 70% by mass of the epoxy resin composition, for example, 53%, 58%, 64%, 69%, etc.;
所述组份(D)占环氧树脂组合物的质量百分比为15％～35％，例如为17％、23％、28％、33％等。The component (D) accounts for 15% to 35% by mass of the epoxy resin composition, for example, 17%, 23%, 28%, 33%, and the like.
本发明的组份(C)氮化硼团聚体，粒径大，具有各向同性，相比片状氮化硼，可以大幅提高体系热导率。The component (C) boron nitride agglomerate of the present invention has a large particle size and isotropic, and the thermal conductivity of the system can be greatly improved as compared with the flaky boron nitride.
根据本发明的环氧树脂组合物，所述组份(D)包括二种不同尺度的颗粒，分别为：According to the epoxy resin composition of the present invention, the component (D) comprises two particles of different sizes, respectively:
(a)D50粒径为30～80nm的纳米无机颗粒物；(a) nano inorganic particles having a D 50 particle size of 30 to 80 nm;
(b)D50粒径为1～10μm的微米无机颗粒物。(b) Micron inorganic particles having a D 50 particle diameter of 1 to 10 μm.
本发明组份(D)的添加可使颗粒大小、形貌相互复配，提高颗粒的填充率，可以提高体系击穿强度等电气性能，并可进一步提高体系的热导率。The addition of the component (D) of the invention enables the particle size and morphology to be compounded with each other, improves the filling rate of the particles, can improve the electrical properties such as the breakdown strength of the system, and can further improve the thermal conductivity of the system.
根据本发明的环氧树脂组合物，所述组份(A)为双酚A环氧树脂、双酚F环氧树脂、脂环族环氧树脂、酚醛环氧树脂或多官能团缩水甘油醚环氧树脂中的一种或两种以上的混合物。According to the epoxy resin composition of the present invention, the component (A) is a bisphenol A epoxy resin, a bisphenol F epoxy resin, an alicyclic epoxy resin, a novolac epoxy resin or a polyfunctional glycidyl ether ring. One or a mixture of two or more of oxygen resins.
优选地，所述组份(A)占环氧树脂组合物的质量百分比为10～25％，例如为12％、15％、18％、23％等。 Preferably, the component (A) accounts for 10 to 25% by mass of the epoxy resin composition, for example, 12%, 15%, 18%, 23%, and the like.
根据本发明的环氧树脂组合物，所述组份(B)为芳香族酸酐、脂环族酸酐、多官能团酸酐或直链脂肪族酸酐中的一种或两种以上的混合物。According to the epoxy resin composition of the present invention, the component (B) is one or a mixture of two or more of an aromatic acid anhydride, an alicyclic acid anhydride, a polyfunctional acid anhydride, or a linear aliphatic acid anhydride.
优选地，所述组份(B)占环氧树脂组合物的质量百分比为5～10％，例如为7％、8.5％、9.4％、9.9％等。Preferably, the component (B) accounts for 5 to 10% by mass of the epoxy resin composition, for example, 7%, 8.5%, 9.4%, 9.9%, and the like.
根据本发明的环氧树脂组合物，所述组份(C)的D50粒径为30～90μm，优选30～70μm。According to the epoxy resin composition of the present invention, the component (C) has a D50 particle diameter of 30 to 90 μm, preferably 30 to 70 μm.
优选地，所述组份(C)占环氧树脂组合物的质量百分比为55～65％。Preferably, the component (C) accounts for 55 to 65% by mass of the epoxy resin composition.
本发明的氮化硼团聚体的制备技术有很多，例如有球粒化造粒法，喷雾造粒法和热压成型法。本发明采用的氮化硼团聚体制备路线简述如下：将500g D50粒径为0.5-4μm的六方氮化硼，10g表面活性剂KH560，450g去离子水经高速搅拌成均匀浆液，加入氢氧化铵缓冲液调节体系pH值为7.8，再加入25g粘结剂聚乙烯醇，经喷雾干燥得到氮化硼团聚体。将所得氮化硼团聚体于氩气保护下于1850℃高温烧结，然后于空气条件下500℃脱碳，得到最终氮化硼团聚体，D50粒径为30-90μm。There are many techniques for preparing boron nitride agglomerates of the present invention, such as spheronization granulation, spray granulation, and hot press molding. The preparation route of the boron nitride agglomerate used in the present invention is as follows: 500 g of hexagonal boron nitride having a D50 particle diameter of 0.5-4 μm, 10 g of surfactant KH560, and 450 g of deionized water are stirred at high speed to form a uniform slurry, and hydroxide is added. The ammonium buffer adjustment system had a pH of 7.8, and 25 g of a binder polyvinyl alcohol was added thereto, followed by spray drying to obtain a boron nitride agglomerate. The obtained boron nitride agglomerates were sintered at a high temperature of 1850 ° C under argon atmosphere, and then decarburized at 500 ° C under air to obtain a final boron nitride agglomerate having a D50 particle size of 30-90 μm.
根据本发明的环氧树脂组合物，所述组份(D)占环氧树脂组合物的质量百分比为20～30％。According to the epoxy resin composition of the present invention, the component (D) accounts for 20 to 30% by mass of the epoxy resin composition.
优选地，所述组份(D)中(a)占所述组份(D)的质量百分比为1～10％，所述组份(D)中(b)占所述组份(D)的质量百分比为90～99％。Preferably, in the component (D), (a) accounts for 1 to 10% by mass of the component (D), and (b) of the component (D) accounts for the component (D). The mass percentage is 90 to 99%.
根据本发明的环氧树脂组合物，所述组分(D)中的(a)纳米无机颗粒物的D50粒径为30～50nm。According to the epoxy resin composition of the present invention, the (a) nano inorganic particles in the component (D) have a D 50 particle diameter of 30 to 50 nm.
优选地，所述组分(D)中的(a)纳米无机颗粒物为球形颗粒，球形度≥0.85，优选≥0.9，进一步优选≥0.95。 Preferably, the (a) nano inorganic particles in the component (D) are spherical particles having a sphericity of ≥ 0.85, preferably ≥ 0.9, further preferably ≥ 0.95.
根据本发明的环氧树脂组合物，所述组分(D)中的(b)微米无机颗粒物的D50粒径为5～10μm。According to the epoxy resin composition of the present invention, the (b) micron inorganic particles in the component (D) have a D 50 particle diameter of 5 to 10 μm.
根据本发明的环氧树脂组合物，所述组分(D)中的(a)纳米无机颗粒物、组分(D)中的(b)微米无机颗粒物各自独立地选自无机氧化物、氮化物或硅酸盐化合物中的任意一种或者两种以上的混合物。According to the epoxy resin composition of the present invention, (a) the nano inorganic particles in the component (D) and the (b) micro inorganic particles in the component (D) are each independently selected from the group consisting of inorganic oxides and nitrides. Or any one or a mixture of two or more of silicate compounds.
优选地，所述氮化物可选为氮化硼(BN)、氮化铝(AlN)或氮化硅(Si3N4)中的任意一种或者两种以上的混合物，优选为氮化硼(BN)。Preferably, the nitride may be selected from any one or a mixture of two or more of boron nitride (BN), aluminum nitride (AlN) or silicon nitride (Si 3 N 4 ), preferably boron nitride. (BN).
优选地，所述无机氧化物可选为氧化铝(Al2O3)、氧化硅(SiO2)、氧化镁(MgO)、氧化锆(ZrO2)或氧化钛(TiO2)中的任意一种或者两种以上的混合物。Preferably, the inorganic oxide may be any one of alumina (Al 2 O 3 ), silicon oxide (SiO 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ) or titanium oxide (TiO 2 ). Kind or a mixture of two or more.
优选地，所述硅酸盐化合物可选为蒙脱石类、蛭石类或云母类化合物中的任意一种或者两种以上的混合物。Preferably, the silicate compound may be selected from any one or a mixture of two or more of montmorillonite, vermiculite or mica.
优选地，所述组分(D)中的(a)纳米无机颗粒物、组分(D)中的(b)微米无机颗粒物各自独立地为BN。Preferably, (a) the nano inorganic particles in the component (D) and the (b) micro inorganic particles in the component (D) are each independently BN.
根据本发明的环氧树脂组合物，所述组份(C)，组分(D)各自独立地经过表面处理。According to the epoxy resin composition of the present invention, the component (C) and the component (D) are each independently subjected to surface treatment.
优选地，所述表面处理采用的表面处理剂为有机硅烷偶联剂。有机硅烷偶联剂是指在硅原子上连接氨基、环氧基等有机基团和烷氧基、酰氧基等水解性基团的化合物。Preferably, the surface treatment agent used for the surface treatment is an organosilane coupling agent. The organosilane coupling agent is a compound in which an organic group such as an amino group or an epoxy group and a hydrolyzable group such as an alkoxy group or an acyloxy group are bonded to a silicon atom.
优选地，所述硅烷偶联剂为有机基团为环氧基的有机硅烷偶联剂，优选为γ～环氧丙氧基丙基三甲氧基硅烷或/和γ～环氧丙氧基丙基三乙氧基硅烷。Preferably, the silane coupling agent is an organosilane coupling agent whose organic group is an epoxy group, preferably γ-glycidoxypropyltrimethoxysilane or/and γ-glycidoxypropane Triethoxy silane.
本发明的目的之一还在于提供本发明所述的导热绝缘环氧树脂组合物的制备方法，包括如下步骤：Another object of the present invention is to provide a method for preparing a thermally conductive and insulating epoxy resin composition according to the present invention, comprising the steps of:
(1)将组份C，组份D经混合机混合均匀，制得填料混合物； (1) Mixing component C and component D uniformly by a mixer to obtain a filler mixture;
(2)将环氧树脂、固化剂、步骤(1)制得的填料混合物、溶剂经超声分散混合均匀，再经高速混合机如VMA-Getzmann公司的高速混合机DISPERMAT进一步混合，高温真空下脱除溶剂，形成未固化环氧组合物；(2) The epoxy resin, the curing agent, the filler mixture prepared in the step (1), and the solvent are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as a high-speed mixer DISPERMAT of VMA-Getzmann, and taken off under high temperature vacuum. Forming an uncured epoxy composition in addition to a solvent;
(3)将未固化环氧组合物倒入已预热的模具中，固化成型。(3) The uncured epoxy composition is poured into a preheated mold and solidified.
根据本发明制备方法，步骤(1)中混合时混合机的转速为500-1000r/min。According to the preparation method of the present invention, the speed of the mixer during mixing in the step (1) is 500-1000 r/min.
根据本发明制备方法，步骤(2)中所述溶剂为丙酮，丁酮，戊酮、二甲苯、二甲基甲酰胺、甲氧基乙醇中的任意一种或者两种以上的混合物，优选为丁酮。According to the preparation method of the present invention, the solvent in the step (2) is any one of acetone, methyl ethyl ketone, pentanone, xylene, dimethylformamide, methoxyethanol or a mixture of two or more, preferably Butanone.
根据本发明制备方法，步骤(3)中固化成型的压力为30-70MPa；According to the preparation method of the present invention, the pressure of the solidification molding in the step (3) is 30-70 MPa;
优选地，固化成型过程为两段固化。Preferably, the curing molding process is two-stage curing.
优选地，第一段固化温度为105～125℃，时间为8～20h；第二段固化温度为130-150℃，时间为7-16h。Preferably, the first stage curing temperature is 105-125 ° C, the time is 8-20 h; the second stage solidification temperature is 130-150 ° C, and the time is 7-16 h.
本发明的目的之一还在于提供本发明所述的环氧树脂组合物的用途，其可用作高压电器如开关柜、变压器、旋转电机、GIS和高密度集成绝缘电子装置如封装系统中的热界面材料。It is also an object of the present invention to provide the use of the epoxy resin composition of the present invention, which can be used as a high voltage electrical appliance such as a switchgear, a transformer, a rotating electrical machine, a GIS, and a high density integrated insulated electronic device such as a packaging system. Thermal interface material.
与已有技术相比，本发明具有如下有益效果：本发明的绝缘环氧树脂组合物具有大于13W/m·K的高热导率，击穿强度大于等于48kV/mm，形状参数大于等于18，可用于高压电器如开关柜、变压器、旋转电机、GIS和高密度集成绝缘电子装置如封装系统中的热界面材料。Compared with the prior art, the present invention has the following beneficial effects: the insulating epoxy resin composition of the present invention has a high thermal conductivity of more than 13 W/m·K, a breakdown strength of 48 kV/mm or more, and a shape parameter of 18 or more. It can be used in high-voltage electrical appliances such as switchgear, transformers, rotating electrical machines, GIS and high-density integrated insulated electronic devices such as thermal interface materials in packaging systems.
具体实施方式detailed description
为更好地说明本发明，便于理解本发明的技术方案，下面对本发明进一步 详细说明。但下述的实施例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and further to the present invention Detailed description. However, the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention, and the scope of the invention is defined by the appended claims.
以下实施例中所用原料如下：The materials used in the following examples are as follows:
日本旭一汽巴公司的CT200型双酚A型环氧树脂；CT200 type bisphenol A epoxy resin of Japan Xuyi Ciba Company;
美国陶氏化学ER113多官能团环氧树脂；American Dow Chemical ER113 polyfunctional epoxy resin;
美国亨斯曼的的CT5532脂环族环氧树脂；CT5532 alicyclic epoxy resin from Huntsman, USA;
日本油墨化学公司的EPICLON B-570脂环族酸酐固化剂；Japan Ink Chemical Company's EPICLON B-570 alicyclic anhydride curing agent;
美国陶氏化学ER314多官能团酸酐固化剂；American Dow Chemical ER314 polyfunctional anhydride curing agent;
昭和电工的片状六方微米氮化硼UHP-1K，UHP-S1；Showa Denko's flake hexagonal micron boron nitride UHP-1K, UHP-S1;
日本古河电子的微米椭球状氮化铝FAN-F05；Japan's Furukawa Electronics' micron ellipsoidal aluminum nitride FAN-F05;
上海水田材料科技有限公司的纳米氮化硼；Nano Boron Nitride from Shanghai Paddy Material Technology Co., Ltd.;
杭州万景新材料有限公司的纳米氧化铝，纳米二氧化硅。Nano-alumina, nano-silica of Hangzhou Wanjing New Material Co., Ltd.
本发明的导热绝缘环氧树脂组合物性能的测试标准如下：The test criteria for the properties of the thermally conductive and insulating epoxy resin composition of the present invention are as follows:
(1)热导率测试(1) Thermal conductivity test
根据GB/T 22588-2008闪光法测量热扩散系数或导热系数中规定的方法进行测试，测试温度为23±2℃，测试5个试样，结果取平均值。According to the method specified in GB/T 22588-2008 flash method for measuring thermal diffusivity or thermal conductivity, the test temperature is 23 ± 2 ° C, 5 samples are tested, and the results are averaged.
(2)击穿强度测试及形状参数(2) Puncture strength test and shape parameters
根据GB/T 1410～2006中5.1规定的方法进行测试，测试温度为23±2℃，测试8个试样。The test was carried out according to the method specified in 5.1 of GB/T 1410-2006. The test temperature was 23 ± 2 ° C, and 8 samples were tested.
采用Weibull分布来计算击穿强度E0和形状参数β。Weibull分布是被广泛用于评价绝缘材料在交流电场下击穿行为的统计规律。二参数Weibull分布的表达式为： The Weibull distribution was used to calculate the breakdown strength E 0 and the shape parameter β. The Weibull distribution is widely used to evaluate the statistical law of the breakdown behavior of insulating materials under alternating electric fields. The expression of the two-parameter Weibull distribution is:
Figure PCTCN2015078193-appb-000001
Figure PCTCN2015078193-appb-000001
式中，P(E)为累积失效概率；E为试样的击穿场强；β为表征数据分散程度的形状因子；E0为P(E)＝63.2％时的击穿场强，也称Weibull击穿场强，用于比较不同试样的电击穿性能。β反映材料击穿场强分布的集中程度β越大，表明材料抗击穿性能越稳定。Where P(E) is the cumulative failure probability; E is the breakdown field strength of the sample; β is the shape factor characterizing the degree of data dispersion; E 0 is the breakdown field strength at P(E)=63.2%, The Weibull breakdown field strength is used to compare the electrical breakdown properties of different samples. The greater the concentration β of the material breakdown field strength distribution, the more stable the material's puncture resistance is.
本发明绝缘环氧树脂组合物性能的具体实施例如下。Specific embodiments of the properties of the insulating epoxy resin composition of the present invention are as follows.
实施例1-5Examples 1-5
根据表1将配方量的组份C氮化硼团聚体，组份D(a)微米片状氮化硼，组份D(b)纳米球形氮化硼经混合机混合均匀，制得填料混合物。将环氧树脂、固化剂、填料混合物、溶剂丁酮经超声分散混合均匀，再经高速混合机如VMA-Getzmann公司的高速混合机DISPERMAT进一步混合，高温真空情况下脱除溶剂，形成未固化环氧组合物。将未固化环氧组合物倒入已预热的模具中，在压力50MPa下固化成型，固化条件为115℃固化15h，然后在140℃固化12h。According to Table 1, the formulation amount of the component C boron nitride agglomerate, the component D (a) micron plate-shaped boron nitride, the component D (b) nano spherical boron nitride were uniformly mixed by a mixer to obtain a filler mixture. . The epoxy resin, the curing agent, the filler mixture and the solvent methyl ethyl ketone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring. Oxygen composition. The uncured epoxy composition was poured into a preheated mold and solidified at a pressure of 50 MPa. The curing conditions were cured at 115 ° C for 15 h and then cured at 140 ° C for 12 h.
本发明实施例1-5中采用的氮化硼团聚体、微米片状氮化硼、纳米球形氮化硼均经过表面处理，表面处理剂为γ～环氧丙氧基丙基三甲氧基硅烷。The boron nitride agglomerate, the micron-plate boron nitride and the nano spherical boron nitride used in the embodiment 1-5 of the invention are all surface-treated, and the surface treatment agent is γ-glycidoxypropyltrimethoxysilane. .
本发明实施例1-5的环氧树脂组合物的配方和性能分别列于表1和表2。The formulations and properties of the epoxy resin compositions of Examples 1-5 of the present invention are shown in Tables 1 and 2, respectively.
表1实施例1-5的环氧树脂组合物配方Table 1 Formulations of Epoxy Resin Compositions of Examples 1-5
Figure PCTCN2015078193-appb-000002
Figure PCTCN2015078193-appb-000002
Figure PCTCN2015078193-appb-000003
Figure PCTCN2015078193-appb-000003
表2实施例1-5的环氧树脂组合物性能Table 2 Performance of Epoxy Resin Compositions of Examples 1-5
Figure PCTCN2015078193-appb-000004
Figure PCTCN2015078193-appb-000004
对比例1-2Comparative example 1-2
根据表3将环氧树脂、固化剂、氮化硼团聚体或微米片状氮化硼、溶剂丁酮经超声分散混合均匀，再经高速混合机如VMA-Getzmann公司的高速混合机DISPERMAT进一步混合，高温真空情况下脱除溶剂，形成未固化环氧组合物。将未固化环氧组合物倒入已预热的模具中，在压力50MPa下固化成型，固化条件为115℃固化15h，然后在140℃固化12h。According to Table 3, epoxy resin, curing agent, boron nitride agglomerate or micron-like boron nitride, solvent butanone are ultrasonically dispersed and uniformly mixed, and then further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT. The solvent is removed under high temperature vacuum to form an uncured epoxy composition. The uncured epoxy composition was poured into a preheated mold and solidified at a pressure of 50 MPa. The curing conditions were cured at 115 ° C for 15 h and then cured at 140 ° C for 12 h.
本发明对比例1-2中采用的氮化硼聚集体、微米片状氮化硼均经过表面处理，表面处理剂为γ～环氧丙氧基丙基三甲氧基硅烷。The boron nitride aggregate and the micron-sized boron nitride used in Comparative Example 1-2 of the present invention are subjected to surface treatment, and the surface treatment agent is γ-glycidoxypropyltrimethoxysilane.
本发明对比例1-2的环氧树脂组合物的配方和性能分别列于表3和表4。The formulations and properties of the epoxy resin compositions of Comparative Examples 1-2 of the present invention are shown in Tables 3 and 4, respectively.
表3对比例1-2的环氧树脂组合物配方Table 3 Comparative Example 1-2 Epoxy Resin Composition Formulation
组份(质量份)Component (parts by mass) 规格specification 对比例1Comparative example 1 对比例2Comparative example 2
环氧树脂Epoxy resin   100100 100100
固化剂Hardener   5252 5252
氮化硼团聚体Boron nitride agglomerate 70μm70μm 650650  
片状氮化硼Flake boron nitride 10μm10μm   650650
表4对比例1-2的环氧树脂组合物性能Table 4 Performance of epoxy resin composition of Comparative Example 1-2
项目project 对比例1Comparative example 1 对比例2Comparative example 2
热导率W/m·KThermal conductivity W/m·K 14.414.4 5.65.6
击穿强度kV/mmBreakdown strength kV/mm 2828 3939
形状参数Shape parameter 8.68.6 13.213.2
从对比例1、2与实施例1-5的比较可以看出：微纳米无机颗粒组合物的可以提高环氧树脂/氮化硼聚集体的击穿强度，形状参数增加说明抗击穿性能稳定，同时保持热导率稳定，达到了导热性能和绝缘性能的平衡。It can be seen from the comparison of Comparative Examples 1, 2 and Examples 1-5 that the micro-nano inorganic particle composition can improve the breakdown strength of the epoxy resin/boron nitride aggregate, and the increase of the shape parameter indicates that the puncture resistance is stable. At the same time, the thermal conductivity is kept stable, and the balance between thermal conductivity and insulation performance is achieved.
实施例6-10Example 6-10
根据表5将配方量的组份C，组份D经混合机混合均匀，制得填料混合物。将环氧树脂、固化剂、填料混合物、溶剂丁酮经超声分散混合均匀，再经高速混合机如VMA-Getzmann公司的高速分散机DISPERMAT进一步混合，高温真空情况下脱除溶剂，形成未固化环氧组合物。将未固化环氧组合物倒入已预热的模具中，在压力30MP下固化成型，固化条件为105℃固化20h，然后在130℃固化16h。According to Table 5, the component A of the formulation amount and the component D were uniformly mixed by a mixer to obtain a filler mixture. The epoxy resin, the curing agent, the filler mixture, the solvent butanone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed disperser DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring. Oxygen composition. The uncured epoxy composition was poured into a preheated mold and solidified under a pressure of 30 MP. The curing conditions were cured at 105 ° C for 20 h and then cured at 130 ° C for 16 h.
本发明实施例6-10中采用的氮化硼聚集体、微米片状氮化硼、微米椭球状 氮化铝、纳米球形氧化铝、纳米球形二氧化硅均经过表面处理，表面处理剂为γ～环氧丙氧基丙基三甲氧基硅烷。Boron nitride aggregates, micron-plate boron nitride, micro-ellipsoids used in Embodiments 6-10 of the present invention The aluminum nitride, the nano-spherical alumina, and the nano-spherical silica are all surface-treated, and the surface treatment agent is γ-glycidoxypropyltrimethoxysilane.
本发明提供的对比例1-2电气绝缘环氧树脂组合物的配方和性能分别列于表5和表6。The formulations and properties of Comparative Example 1-2 Electrically Insulating Epoxy Resin Compositions Provided by the Invention are listed in Tables 5 and 6, respectively.
表5实施例6-10的环氧树脂组合物配方Table 5 Formulations of Epoxy Resin Compositions of Examples 6-10
Figure PCTCN2015078193-appb-000005
Figure PCTCN2015078193-appb-000005
表6实施例6-10的环氧树脂组合物性能Table 6 Performance of Epoxy Resin Compositions of Examples 6-10
Figure PCTCN2015078193-appb-000006
Figure PCTCN2015078193-appb-000006
实施例11-15Example 11-15
根据表1将配方量的组份C氮化硼团聚体，组份D(a)微米片状氮化硼，组份D(b)纳米球形氮化硼经混合机混合均匀，制得填料混合物。将环氧树脂、固化剂、填料混合物、溶剂丁酮经超声分散混合均匀，再经高速混合机如VMA-Getzmann公司的高速混合机DISPERMAT进一步混合，高温真空情况下脱除溶剂，形成未固化环氧组合物。将未固化环氧组合物倒入已预热的模具中，在压力70MP下固化成型，固化条件为125℃固化8h，然后在150℃固化7h。According to Table 1, the formulation amount of the component C boron nitride agglomerate, the component D (a) micron plate-shaped boron nitride, the component D (b) nano spherical boron nitride were uniformly mixed by a mixer to obtain a filler mixture. . The epoxy resin, the curing agent, the filler mixture and the solvent methyl ethyl ketone are uniformly dispersed by ultrasonication, and further mixed by a high-speed mixer such as VERA-Getzmann's high-speed mixer DISPERMAT, and the solvent is removed under high temperature vacuum to form an uncured ring. Oxygen composition. The uncured epoxy composition was poured into a preheated mold and solidified under a pressure of 70 MP. The curing conditions were cured at 125 ° C for 8 h and then cured at 150 ° C for 7 h.
本发明实施例11-15的环氧树脂组合物的配方和性能分别列于表7和表8。The formulations and properties of the epoxy resin compositions of Examples 11-15 of the present invention are listed in Tables 7 and 8, respectively.
表7实施例11-15的环氧树脂组合物配方Table 7 Formulations of Epoxy Resin Compositions of Examples 11-15
Figure PCTCN2015078193-appb-000007
Figure PCTCN2015078193-appb-000007
表8实施例11-15的环氧树脂组合物性能Table 8 Performance of Epoxy Resin Compositions of Examples 11-15
Figure PCTCN2015078193-appb-000008
Figure PCTCN2015078193-appb-000008
Figure PCTCN2015078193-appb-000009
Figure PCTCN2015078193-appb-000009
申请人声明，本发明通过上述实施例来说明本发明的工艺方法，但本发明并不局限于上述工艺步骤，即不意位着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The Applicant declares that the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it is not intended that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。 In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (10)

  1. 一种高导热绝缘环氧树脂组合物，其特征在于，包括如下组分：A high thermal conductive insulating epoxy resin composition comprising the following components:
    (A)一种或两种以上的环氧树脂；(A) one or two or more epoxy resins;
    (B)一种或两种以上的酸酐固化剂；(B) one or two or more acid anhydride curing agents;
    (C)氮化硼团聚体；(C) boron nitride agglomerates;
    (D)微纳米无机颗粒组合物；(D) a micro-nano inorganic particle composition;
    所述组份(C)占环氧树脂组合物的质量百分比为50％～70％；The component (C) accounts for 50% to 70% by mass of the epoxy resin composition;
    所述组份(D)占环氧树脂组合物的质量百分比为15％～35％。The component (D) accounts for 15% to 35% by mass of the epoxy resin composition.
  2. 根据权利要求1所述的环氧树脂组合物，其特征在于，所述组份(D)包括二种不同尺度的颗粒，分别为：The epoxy resin composition according to claim 1, wherein said component (D) comprises two particles of different sizes, respectively:
    (a)D50粒径为30～80nm的纳米无机颗粒物；(a) nano inorganic particles having a D 50 particle size of 30 to 80 nm;
    (b)D50粒径为1～10μm的微米无机颗粒物。(b) Micron inorganic particles having a D 50 particle diameter of 1 to 10 μm.
  3. 根据权利要求1或2所述的环氧树脂组合物，其特征在于，所述组份(A)为双酚A环氧树脂、双酚F环氧树脂、脂环族环氧树脂、酚醛环氧树脂或多官能团缩水甘油醚环氧树脂中的一种或两种以上的混合物；The epoxy resin composition according to claim 1 or 2, wherein the component (A) is a bisphenol A epoxy resin, a bisphenol F epoxy resin, an alicyclic epoxy resin, or a phenolic ring. One or a mixture of two or more of an oxyresin or a polyfunctional glycidyl ether epoxy resin;
    优选地，所述组份(A)占环氧树脂组合物的质量百分比为10～25％。Preferably, the component (A) accounts for 10 to 25% by mass of the epoxy resin composition.
  4. 根据权利要求1-3任一项所述的环氧树脂组合物，其特征在于，所述组份(B)为芳香族酸酐、脂环族酸酐、多官能团酸酐或直链脂肪族酸酐中的一种或两种以上的混合物；The epoxy resin composition according to any one of claims 1 to 3, wherein the component (B) is an aromatic acid anhydride, an alicyclic acid anhydride, a polyfunctional acid anhydride or a linear aliphatic acid anhydride. One or a mixture of two or more;
    优选地，所述组份(B)占环氧树脂组合物的质量百分比为5～10％。Preferably, the component (B) accounts for 5 to 10% by mass of the epoxy resin composition.
  5. 根据权利要求1-4任一项所述的环氧树脂组合物，其特征在于，所述组份(C)的D50粒径为30～90μm，优选30～70μm；The epoxy resin composition according to any one of claims 1 to 4, wherein the component (C) has a D50 particle size of 30 to 90 μm, preferably 30 to 70 μm;
    优选地，所述组份(C)占环氧树脂组合物的质量百分比为55～65％。Preferably, the component (C) accounts for 55 to 65% by mass of the epoxy resin composition.
  6. 根据权利要求1-5任一项所述的环氧树脂组合物，其特征在于，所述组 份(D)占环氧树脂组合物的质量百分比为20～30％；The epoxy resin composition according to any one of claims 1 to 5, wherein the group The portion (D) accounts for 20 to 30% by mass of the epoxy resin composition;
    优选地，所述组份(D)中(a)占所述组份(D)的质量百分比为1～10％，所述组份(D)中(b)占所述组份(D)的质量百分比为90～99％；Preferably, in the component (D), (a) accounts for 1 to 10% by mass of the component (D), and (b) of the component (D) accounts for the component (D). The mass percentage is 90 to 99%;
    优选地，所述组份(D)中的(a)纳米无机颗粒物的D50粒径为30～50nm；Preferably, the (a) nano inorganic particles in the component (D) have a D 50 particle size of 30 to 50 nm;
    优选地，所述组份(D)中的(a)纳米无机颗粒物为球形颗粒，球形度≥0.85，优选≥0.9，进一步优选≥0.95；Preferably, the (a) nano inorganic particles in the component (D) are spherical particles having a sphericity of ≥ 0.85, preferably ≥ 0.9, further preferably ≥ 0.95;
    优选地，所述组份(D)中的(b)微米无机颗粒物的D50粒径为5～10μm。Preferably, the (b) micron inorganic particles in the component (D) have a D 50 particle diameter of 5 to 10 μm.
  7. 根据权利要求1-6任一项所述的环氧树脂组合物，其特征在于，所述组份(D)中的(a)纳米无机颗粒物、(b)微米无机颗粒物各自独立地选自无机氧化物、氮化物或硅酸盐化合物中的任意一种或者两种以上的混合物；The epoxy resin composition according to any one of claims 1 to 6, wherein (a) the nano inorganic particles and (b) the micro inorganic particles in the component (D) are each independently selected from the group consisting of inorganic Any one or a mixture of two or more of an oxide, a nitride or a silicate compound;
    优选地，所述氮化物可选为氮化硼、氮化铝或氮化硅中的任意一种或者两种以上的混合物，优选为氮化硼；Preferably, the nitride may be selected from any one or a mixture of two or more of boron nitride, aluminum nitride or silicon nitride, preferably boron nitride;
    优选地，所述无机氧化物可选为氧化铝、氧化硅、氧化镁、氧化锆或氧化钛中的任意一种或者两种以上的混合物；Preferably, the inorganic oxide may be selected from any one or a mixture of two or more of alumina, silica, magnesia, zirconia or titania;
    优选地，所述硅酸盐化合物可选为蒙脱石类、蛭石类或云母类化合物中的任意一种或者两种以上的混合物；Preferably, the silicate compound may be selected from any one or a mixture of two or more of montmorillonite, vermiculite or mica;
    优选地，所述组分(D)中的(a)纳米无机颗粒物、(b)微米无机颗粒物各自独立地为氮化硼。Preferably, (a) the nano inorganic particles and (b) the micro inorganic particles in the component (D) are each independently boron nitride.
  8. 根据权利要求1-7任一项所述的环氧树脂组合物，其特征在于，所述组份(C)，组分(D)各自独立地经过表面处理；The epoxy resin composition according to any one of claims 1 to 7, wherein the component (C) and the component (D) are each independently subjected to surface treatment;
    优选地，所述表面处理采用的表面处理剂为有机硅烷偶联剂；Preferably, the surface treatment agent used for the surface treatment is an organosilane coupling agent;
    优选地，所述硅烷偶联剂为有机基团为环氧基的有机硅烷偶联剂，优选为γ～环氧丙氧基丙基三甲氧基硅烷或/和γ～环氧丙氧基丙基三乙氧基硅烷。 Preferably, the silane coupling agent is an organosilane coupling agent whose organic group is an epoxy group, preferably γ-glycidoxypropyltrimethoxysilane or/and γ-glycidoxypropane Triethoxy silane.
  9. 权利要求1-8任一项所述的导热绝缘环氧树脂组合物的制备方法，包括如下步骤：The method for preparing a thermally conductive and insulating epoxy resin composition according to any one of claims 1 to 8, comprising the steps of:
    (1)将组份C，组份D经混合机混合均匀，制得填料混合物；(1) Mixing component C and component D uniformly by a mixer to obtain a filler mixture;
    (2)将环氧树脂、固化剂、步骤(1)制得的填料混合物、溶剂经超声分散混合均匀，再进一步混合，高温真空下脱除溶剂，形成未固化环氧组合物；(2) The epoxy resin, the curing agent, the filler mixture prepared in the step (1), and the solvent are uniformly dispersed by ultrasonic dispersion, further mixed, and the solvent is removed under high temperature vacuum to form an uncured epoxy composition;
    (3)将未固化环氧组合物倒入已预热的模具中，固化成型；(3) pouring the uncured epoxy composition into a preheated mold, and solidifying and molding;
    优选地，步骤(1)中混合时混合机的转速为500-1000r/min；Preferably, the speed of the mixer when mixing in step (1) is 500-1000r/min;
    优选地，步骤(2)中所述溶剂为丙酮、丁酮、戊酮、二甲苯、二甲基甲酰胺、甲氧基乙醇中的任意一种或者两种以上的混合物，优选为丁酮；Preferably, the solvent in the step (2) is any one of acetone, methyl ethyl ketone, pentanone, xylene, dimethylformamide, methoxyethanol or a mixture of two or more, preferably butanone;
    优选地，步骤(2)中的混合采用高速混合机进行；Preferably, the mixing in step (2) is carried out using a high speed mixer;
    优选地，步骤(3)中固化成型的压力为30-70MPa；Preferably, the pressure of solidification molding in step (3) is 30-70 MPa;
    优选地，固化成型为两段固化；Preferably, the curing is formed into two-stage curing;
    优选地，第一段固化温度为105～125℃，时间为8～20h；第二段固化温度为130-150℃，时间为7-16h。Preferably, the first stage curing temperature is 105-125 ° C, the time is 8-20 h; the second stage solidification temperature is 130-150 ° C, and the time is 7-16 h.
  10. 权利要求1-8任一项所述的环氧树脂组合物的用途，其特征在于，其用作高压电器或高密度集成绝缘电子装置中的热界面材料。 Use of an epoxy resin composition according to any of claims 1-8, characterized in that it is used as a thermal interface material in high voltage electrical appliances or high density integrated insulated electronic devices.
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