WO2018230638A1 - Nitrure de bore modifié par du carbone, procédé pour sa production et composition de résine hautement thermoconductrice - Google Patents

Nitrure de bore modifié par du carbone, procédé pour sa production et composition de résine hautement thermoconductrice Download PDF

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WO2018230638A1
WO2018230638A1 PCT/JP2018/022717 JP2018022717W WO2018230638A1 WO 2018230638 A1 WO2018230638 A1 WO 2018230638A1 JP 2018022717 W JP2018022717 W JP 2018022717W WO 2018230638 A1 WO2018230638 A1 WO 2018230638A1
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boron nitride
carbon
graphene oxide
resin
modified boron
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PCT/JP2018/022717
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English (en)
Japanese (ja)
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弘朗 在間
伊藤　玄
淳子 大仲
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株式会社Kri
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Priority claimed from JP2018106168A external-priority patent/JP6803874B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a high thermal conductive material composed of boron nitride and a resin, and specifically to a surface-modified boron nitride.
  • nitrides such as boron nitride having no electrical conductivity and high thermal conductivity are expected.
  • the boron nitride surface has very few functional groups, the affinity with the resin is low. For this reason, there are problems that the dispersibility in the resin is poor, and that separation occurs at the interface between the boron nitride surface and the resin and voids are easily formed.
  • a silane coupling agent, an organic compound, or the like is reacted with an amino group or a hydroxyl group in boron nitride.
  • these groups are mainly present on the end face of the boron nitride crystal sheet having a layered structure similar to that of graphite, it is not very effective in improving the resin affinity on the boron nitride surface.
  • Patent Document 1 heating oxidation in air (Patent Document 1), surface oxidation using supercritical water or subcritical water (Patent Document 2), and introduction of amino groups by plasma treatment (Patent Document 1).
  • Patent Document 3 mechanochemical treatment
  • Patent Document 4 mechanochemical treatment
  • the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide boron nitride having good resin compatibility with energy saving, low cost.
  • Another object is to provide a high thermal conductive resin composition by mixing the carbon-modified boron nitride with a resin.
  • the carbon-modified boron nitride of the present invention has a sheet-like carbon layer on the surface of boron nitride particles.
  • the sheet-like carbon layer is 1 to 20 layers of graphene oxide, or the sheet-like carbon layer is 1 to 20 layers of reduced graphene oxide.
  • the high thermal conductive resin composition of the present invention includes the above carbon-modified boron nitride and a resin.
  • the method for producing carbon-modified boron nitride particles of the present invention includes a step of mixing an aqueous graphene oxide dispersion and boron nitride powder, and collecting and drying a solid from the liquid obtained by the mixing, and carbon-modified boron nitride. Obtaining.
  • the method further includes the step of reducing the carbon-modified boron nitride with a reducing agent.
  • boron nitride having a sheet-like carbon layer on the particle surface can be provided with energy saving and low cost.
  • the affinity between boron nitride and the resin is improved, the fluidity of the blended resin composition and the interfacial adhesion between the boron nitride and the resin can be improved.
  • a heat conductive resin composition having no electrical conductivity and excellent mechanical strength and thermal conductivity.
  • the carbon-modified boron nitride of the present invention has a sheet-like carbon layer on the surface of the boron nitride particles, and this sheet-like carbon layer has a function of improving the affinity between the resin and the boron nitride interface.
  • the sheet-like carbon layer is graphene oxide or reduced graphene oxide obtained by subjecting this graphene oxide to chemical reduction and / or physical reduction treatment by heating. Any known technique can be used for the reduction method, and there is no particular limitation.
  • the sheet-like carbon layer is graphene oxide or reduced graphene oxide obtained by reducing the sheet carbon layer can be selected depending on the properties of the resin mixed with the carbon-modified boron nitride.
  • the affinity for a resin to be mixed can be improved using these.
  • a method of use a method of chemically bonding these groups to a resin, a method of using physical interaction between these groups and a functional group in the resin molecule, an organic compound having good affinity with the resin for these groups, or Examples include a method of chemically bonding oligomers.
  • Graphene oxide obtained by oxidizing and exfoliating graphite using the Hammers method is a single layer graphene oxide, multi-layer graphene oxide composed of multiple layers of single-layer graphene oxide, and multi-layer oxidation with a non-oxidized layer inside It becomes a mixture of graphene. In this specification, all of these are referred to as graphene oxide. If such a mixture is used as it is, the sheet-like carbon layer becomes a layer in which single-layer to multi-layer graphene oxide is mixed.
  • the function of the sheet-like carbon layer is exhibited by 1 to 20 layers, preferably 1 to 10 layers, more preferably 1 to 7 layers of graphene oxide or reduced graphene oxide. If it exceeds 20 layers, the properties of graphite become dominant and the effects of the present invention may not be exhibited.
  • the number of layers of graphene oxide and reduced graphene oxide can be evaluated by, for example, an atomic force microscope, a transmission electron microscope, a Raman spectrum, or the like.
  • This coverage ratio can be estimated from X-ray photoelectron spectroscopy. Further, a micro Raman spectrum measurement of a plurality of points is performed, and the coverage ratio can be obtained by using a ratio of the number of points at which D or G bands derived from graphene oxide are observed to the total number of measurement points. Also in this case, the covering ratio is at least 0.2 or more, preferably 0.3 or more, more preferably 0.5 or more.
  • the sheet-like carbon layer is typically laminated by being adsorbed on boron nitride particles.
  • Boron nitride has various crystal structures such as hexagonal crystal and cubic crystal, and any of them can be used in the present invention.
  • hexagonal boron nitride powder is preferable because it is easily available industrially and is inexpensive.
  • the size of boron nitride is not particularly limited as long as it is generally suitable for use in the heat conduction field.
  • the average particle diameter is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.5 ⁇ m to 60 ⁇ m. When the average particle size is smaller than 0.1 ⁇ m, the fluidity of the resin composition obtained by strengthening the nanoparticle effect may be lowered.
  • the layer thickness in the case of forming a heat conductive layer from the obtained resin composition may not be sufficiently reduced.
  • an average particle diameter (d50) measured by a laser diffraction / scattering method can be adopted.
  • graphene oxide 0.01 w% to 5 w% aqueous dispersion obtained by oxidizing graphite using a known method known as the Hummers method and performing exfoliation treatment to 1 to 20 layers can be used.
  • the medium hydrophilic solvents such as alcohols such as methanol and ethanol, glycols such as ethylene glycol, tetrahydrofuran and the like can be added as long as graphene oxide is mainly agglomerated and does not aggregate.
  • the graphene oxide obtained has various shapes, but the general shape is a thin sheet with a shape close to a rectangle with irregularities around it, the size of which depends on the size of the raw graphite crystals To do.
  • the longest length of the existing sheet is the average particle size of boron nitride particles
  • the diameter is 1/1000 to 2/1, preferably 1/500 to 1/1, and more preferably 1/10 to 0.7 / 1. When it is out of the range of 1/1000 to 2/1, it is difficult to form a sheet-like carbon layer.
  • Carbon-modified boron nitride is dispersed in graphene oxide aqueous dispersion by adding boron nitride powder and stirring or using a powerful dispersing device such as a homogenizer as necessary, and then recovered from the dispersion by filtration or centrifugal sedimentation. Then, it can obtain as a powder by drying at room temperature or heat-drying as needed.
  • boron nitride powder is dispersed in an aqueous graphene oxide dispersion, precipitation occurs and the color of the supernatant (graphene oxide aqueous dispersion layer) becomes lighter. Finally, the supernatant becomes colorless and transparent, and graphene oxide is not detected from the supernatant.
  • the amount of boron nitride added to the graphene oxide aqueous dispersion can be arbitrarily selected depending on how much boron nitride is adsorbed on the surface of the boron nitride particles.
  • the sheet-like carbon layer can be converted into reduced graphene oxide by chemical reduction in which the dispersion or the dried product is reduced with a reducing agent, or heat reduction in which the dried product is heat-treated.
  • a reducing agent for chemical reduction known ones can be used.
  • hydrazine, hydrazine reducing agents such as hydrazine compounds such as hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, sodium borohydride, sodium sulfite, Sodium bisulfite, sodium thiosulfate, sodium nitrite, sodium hyponitrite, phosphorous acid and its salts such as sodium phosphite, hypophosphorous acid and its salts such as sodium hypophosphite, hydrogen iodide, ascorbine
  • phosphorous acid and its salts such as sodium phosphite, hypophosphorous acid and its salts such as sodium hypophosphite, hydrogen iodide, ascorbine
  • acids include acids, alcohols such as ethanol, glycols such as ethylene glycol, and the like, and one or more of these can be used.
  • the amount used is preferably 0.1 to 50 times, preferably 0.5 to 30 times, more preferably 1 to 20 times the weight of graphene oxide. If the total amount of the reducing agent is less than the above range, the reaction may not proceed easily, and if it exceeds the above range, it may take time to remove from the system.
  • the reduction time is 1 hour to 72 hours when the reduction is performed at room temperature.
  • the reaction mixture can be heated to facilitate the reduction.
  • the heating range is 30 ° C to 100 ° C, preferably 40 ° C to 90 ° C, more preferably 50 ° C to 80 ° C.
  • known conditions can be used. For example, heat treatment may be performed at 700 ° C. to 1200 ° C. in a vacuum or an inert gas.
  • the high thermal conductive resin composition of the present invention includes the above carbon-modified boron nitride and a resin.
  • the high thermal conductive resin composition can be obtained by mixing carbon-modified boron nitride and a resin.
  • the amount of carbon-modified boron nitride mixed with the resin is typically 1% to 90% by volume, preferably 10% to 90% by volume, more preferably 20% to 90% by volume. If the mixing amount is less than 1% by volume, thermal conductivity may not be obtained.
  • the method of mixing the carbon-modified boron nitride of the present invention with a resin is a dry process in which, when the resin is a solid, the carbon-modified boron nitride and the carbon-modified boron nitride are mixed with powder and then melt mixed using a kneader or a twin screw extruder. Alternatively, it can be carried out by a wet process in which a resin is dissolved in an appropriate solvent and mixed with carbon-modified boron nitride and stirred or dispersed using a homogenizer or bead mill. These methods can be appropriately selected depending on the properties of the resin used.
  • the resin is liquid, mix it with carbon-modified boron nitride using a stirrer, three-roll or kneader, or mix and stir the resin with carbon-modified boron nitride by diluting the resin with an appropriate solvent or diluent.
  • a mixing process can be performed by a dispersion process using a homogenizer or a bead mill. These methods can be appropriately selected depending on the properties of the resin used.
  • the resin examples include polyolefin, polycycloolefin, polystyrene, ABS, polycarbonate, polyamide, polyimide, polyacrylate, polyethylene terephthalate, polyphenylene sulfide, epoxy resin, urethane resin, silicone resin, phenol resin, and the like.
  • the resin composition may further contain a curing agent, a crosslinking agent, a polymerization initiator, a high molecular compound or a low molecular compound for adjusting physical properties, and an inorganic filler such as silica or clay as necessary.
  • the oxidized graphite was diluted with 100 ml of a mixed solution adjusted to have a hydrogen peroxide concentration of 0.5% and a sulfuric acid concentration of 3%, and the oxidized graphite was centrifuged. The precipitate was again dispersed in 100 ml of a mixture containing 0.5% hydrogen peroxide and 3% sulfuric acid, and then centrifuged to obtain graphite oxide.
  • the centrifugal sediment is dispersed in 100 ml of a mixture containing 0.5% hydrogen peroxide and 3% sulfuric acid, placed in a dialysis membrane, soaked in ion-exchanged water, and exchanged ion-exchanged water for 7 days. Dialysis was performed. Next, the dialysate was put into an ultrasonic cleaner and subjected to ultrasonic irradiation for 8 hours, and then the supernatant was taken out by centrifugation to obtain a graphene oxide dispersion having a concentration of 0.044 g / 100 ml.
  • the longest sheet has a length distribution of 100 nm to 2000 nm and a thickness of 1 nm to 18 nm. The object was observed.
  • Example 1 (Production of carbon-modified boron nitride having a graphene oxide layer) Hexagonal boron nitride powder (Showa Denko Shobinu (registered trademark) UHP-2) was added to 50 ml of a 0.044 g / 100 ml graphene oxide dispersion while irradiating ultrasonic waves with an ultrasonic cleaner.
  • Hexagonal boron nitride powder Showa Denko Shobinu (registered trademark) UHP-2
  • boron nitride powder was added, coagulation precipitation occurred, and as the amount added increased, the color of the supernatant (brown) became lighter, and when 7.5 g of boron nitride powder was added, the supernatant became almost colorless.
  • the precipitate was separated by filtration, washed with 100 ml of distilled water and 100 ml of methanol, and dried at 60 ° C. for 8 hours to obtain a light brown powder (referred to as carbon-modified UHP-2).
  • carbon-modified UHP-2 a light brown powder
  • this powder was observed with a field emission scanning electron microscope, many wrinkles were observed on the surface of the flat boron nitride particles as shown in FIG. Since such a soot is not seen in the raw material boron nitride particles, this soot is considered to be due to the graphene oxide formed on the surface of the boron nitride particles.
  • Example 2 Production of carbon-modified boron nitride having a reduced graphene oxide layer
  • hexagonal boron nitride powder While adding hexagonal boron nitride powder to 50 ml of a 0.044 g / 100 ml graphene oxide dispersion, it was added.
  • boron nitride powder was added, coagulation precipitation occurred, and as the amount added increased, the color of the supernatant (brown) became lighter, and when 7.5 g of boron nitride powder was added, the supernatant became almost colorless.
  • 5 ml of hydrazine hydrate was added and stirred overnight at room temperature.
  • the formed precipitate was filtered off, washed with 100 ml of distilled water and 100 ml of methanol, and then dried at 60 ° C. for 8 hours to obtain a gray powder (reduced form).
  • Carbon modified UHP-2 When micro Raman spectra were measured at five different points on the surface of the dried boron nitride particles, the G band of reduced graphene oxide could be observed at all measurement points. Therefore, nitriding covered with reduced graphene oxide was performed. It is considered that boron particles are obtained.
  • Example 3 Preparation of resin composition containing carbon-modified boron nitride 1
  • 33 parts by weight of bis-A type epoxy Mitsubishi Chemical: Ep828)
  • 19 parts by weight of phenol novolak DIC: TD2090
  • 2-ethyl-4-methylimidazole Nacalai Tesque: 2E4MZ
  • 48 parts by weight of carbon-modified UHP-2 prepared in Example 1 was added and kneaded until uniform in a mortar to obtain a boron nitride mixture (the boron nitride addition amount was 35 vol%).
  • the obtained mixture was dried at 120 ° C. for 4 minutes, and pressed with a vacuum press at 140 ° C./0.5 MPa / 5 minutes and 180 ° C./0.5 MPa / 2 hours to obtain a cured product.
  • Example 4 (Preparation of resin composition containing carbon-modified boron nitride 2) A cured epoxy resin was obtained in the same manner as in Example 3 except that the amount of carbon-modified UHP-2 prepared in Example 1 was changed to 45 vol%.
  • Comparative Example 2 A cured epoxy resin was prepared in the same manner as in Comparative Example 1, except that the amount of boron nitride (Showen D (registered trademark) UHP-2 manufactured by Showa Denko) was 45 vol%.
  • boron nitride Showen D (registered trademark) UHP-2 manufactured by Showa Denko
  • Example 3 and Comparative Example 1 and Example 4 and Comparative Example 2 having the same addition amount are compared, the cured product using carbon-modified boron nitride clearly has a thickness direction and a planar direction. Both had improved thermal conductivity. In particular, the thermal conductivity in the thickness direction was greatly improved by 23% in Example 2. The reason why the thermal conductivity is different between the planar direction and the thickness direction in the produced cured product is considered to be because boron nitride is oriented in the planar direction.
  • the cause of the improvement in the thermal conductivity in the thickness direction in particular was considered to be that the affinity between the boron nitride surface and the resin was improved, resulting in a decrease in void formation due to separation at the interface between the two. .
  • Example 5 Preparation of resin composition containing carbon-modified boron nitride 3 20 parts by weight of bis-A type epoxy (Mitsubishi Chemical: Ep828), 11 parts by weight of phenol novolac (DIC: TD2090), and 0.3 parts by weight of 2-ethyl-4-methylimidazole (Nacalai Tesque: 2E4MZ) are used in a mortar.
  • Example 2 38 parts by weight of carbon-modified UHP-2 prepared in Example 1 and 31 parts by weight of spherical alumina CB A20S were added and kneaded until uniform in a mortar to obtain a boron nitride-alumina mixture (nitriding)
  • the boron addition amount is 35 vol%
  • the alumina addition amount is 15 vol%
  • the total filler addition amount is 50 vol%).
  • the obtained mixture was dried at 120 ° C. for 4 minutes, and pressed with a vacuum press at 140 ° C./20 MPa / 5 minutes and 180 ° C./0.5 MPa / 2 hours to obtain a cured product.
  • the thermal diffusivity in the thickness direction and the plane direction was measured using a Bethel thermowave analyzer TA (periodic heating method), and the thermal conductivity in the thickness direction and the plane direction was calculated from the specific heat and specific gravity of the cured product. .
  • Example 6 (Preparation of resin composition containing carbon-modified boron nitride 2-5) Spherical alumina (A cured epoxy resin was prepared in the same manner as in Example 5 except that the amount of CB A20S manufactured by Showa Denko was changed to 25, 35, and 40 vol% according to Table 2, and the thermal conductivity in the thickness direction and the planar direction was produced. was calculated.
  • Example 5 and Comparative Example 3 and Example 6 and Comparative Example 4 having the same addition amount are compared, the cured product using carbon-modified boron nitride clearly has a thickness direction.
  • the thermal conductivity was improved in the plane direction.
  • the heat conductivity in the thickness direction was greatly improved by 61% in Example 8. The reason why the thermal conductivity is different between the planar direction and the thickness direction in the produced cured product is considered to be because boron nitride is oriented in the planar direction.
  • the factors that particularly improved the thermal conductivity in the thickness direction were that the addition of spherical alumina disturbed the planar orientation of boron nitride, increasing the heat path in the thickness direction, and the surface of the boron nitride surface.
  • the affinity between the resin and the resin it is considered that void formation due to separation at the interface between the two has decreased.
  • Example 9 (Preparation of resin composition containing carbon-modified boron nitride 6) Solvent-free silicone resin (KNS-320A manufactured by Shin-Etsu Chemical Co., Ltd.) 1.56 parts by weight and 2.18 parts by weight of carbon-modified boron nitride prepared in Example 1 and a curing agent (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) 0 .03 parts by weight were mixed well in a mortar. The mixture was put into a square container made of polytetrafluoroethylene and subjected to vacuum degassing (room temperature 30 minutes), then the lid was spread with a plate made of polytetrafluoroethylene, covered and heated at 80 ° C.
  • KNS-320A manufactured by Shin-Etsu Chemical Co., Ltd. Solvent-free silicone resin
  • CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
  • the obtained cured product is taken out from the mold, and the thermal diffusivity in the thickness direction is measured using Bethel Thermowave Analyzer TA (periodic heating method), and the thermal conductivity in the thickness direction is determined from the specific heat and specific gravity of the cured product. When calculated, the thermal conductivity was 1.31 W / (m ⁇ K).
  • Example 7 A cured product was prepared in the same manner as in Example 9 except that the carbon-modified boron nitride was changed to unmodified boron nitride (Showa Denko (registered trademark) UHP-2), and the thermal conductivity in the thickness direction was calculated. As a result, the thermal conductivity was 0.82 W / (m ⁇ K). Compared with Example 9, the heat conductivity was higher when carbon-modified boron nitride was used.
  • the carbon-modified boron nitride of the present invention has a sheet-like carbon layer on the particle surface, thereby improving the affinity with the resin and improving the fluidity of the blended resin composition and the interfacial adhesion between the boron nitride and the resin. can do.
  • the heat conductive resin composition excellent in mechanical strength and heat conductivity can be provided, and can be used as a heat conductive material and a heat dissipation material for various devices.

Abstract

L'invention concerne un nitrure de bore modifié par du carbone à conservation d'énergie présentant une bonne affinité pour la résine, présentant une couche de carbone de type feuille sur la surface de particule. L'invention concerne également une composition de résine hautement thermoconductrice contenant le nitrure de bore modifié par du carbone et une résine. Ce nitrure de bore modifié par du carbone présente une couche de carbone de type feuille sur la surface de particule de nitrure de bore, une couche de carbone de type feuille préférée étant constituée par 1-20 couches d'oxyde de graphène ou par 1-20 couches d'oxyde de graphène réduit.
PCT/JP2018/022717 2017-06-16 2018-06-14 Nitrure de bore modifié par du carbone, procédé pour sa production et composition de résine hautement thermoconductrice WO2018230638A1 (fr)

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JP2017-118255 2017-06-16
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JP2018-106168 2018-06-01
JP2018106168A JP6803874B2 (ja) 2017-06-16 2018-06-01 カーボン修飾窒化ホウ素、その製造方法および高熱伝導性樹脂組成物

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CN110451498A (zh) * 2019-09-09 2019-11-15 吉林大学 一种石墨烯-氮化硼纳米片复合结构及其制备方法
CN110510604A (zh) * 2019-09-09 2019-11-29 吉林大学 一种石墨烯/氮化硼层状异质结构及其制备方法
CN112812341A (zh) * 2021-02-09 2021-05-18 桂林电子科技大学 一种高导热四针状结构复合微粒/聚酰亚胺薄膜及其制备方法

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JP2013008680A (ja) * 2010-11-24 2013-01-10 Fuji Electric Co Ltd グラフェンを含む導電性薄膜および透明導電膜
JP2014522321A (ja) * 2011-03-22 2014-09-04 ユニバーシティ・オブ・マンチェスター グラフェンに関する構造体および方法
WO2014171030A1 (fr) * 2013-04-19 2014-10-23 株式会社インキュベーション・アライアンス Fibres de carbone et leur procédé de production
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110451498A (zh) * 2019-09-09 2019-11-15 吉林大学 一种石墨烯-氮化硼纳米片复合结构及其制备方法
CN110510604A (zh) * 2019-09-09 2019-11-29 吉林大学 一种石墨烯/氮化硼层状异质结构及其制备方法
CN110510604B (zh) * 2019-09-09 2022-11-18 吉林大学 一种石墨烯/氮化硼层状异质结构及其制备方法
CN112812341A (zh) * 2021-02-09 2021-05-18 桂林电子科技大学 一种高导热四针状结构复合微粒/聚酰亚胺薄膜及其制备方法

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