WO2021230608A1 - Procédé de préparation de matériau de chauffage composite au moyen de fibres de carbone revêtues de métal et matériau de chauffage composite préparé par ledit procédé - Google Patents

Procédé de préparation de matériau de chauffage composite au moyen de fibres de carbone revêtues de métal et matériau de chauffage composite préparé par ledit procédé Download PDF

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WO2021230608A1
WO2021230608A1 PCT/KR2021/005853 KR2021005853W WO2021230608A1 WO 2021230608 A1 WO2021230608 A1 WO 2021230608A1 KR 2021005853 W KR2021005853 W KR 2021005853W WO 2021230608 A1 WO2021230608 A1 WO 2021230608A1
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Prior art keywords
metal
carbon fiber
composite material
resin
coated carbon
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PCT/KR2021/005853
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English (en)
Korean (ko)
Inventor
이종길
허수형
정용희
한송희
김재환
Original Assignee
주식회사 비에스엠신소재
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Publication of WO2021230608A1 publication Critical patent/WO2021230608A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/18—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor the conductor being embedded in an insulating material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
    • H05B2203/017—Manufacturing methods or apparatus for heaters

Definitions

  • the present invention relates to a method for manufacturing a heating composite material using a metal-coated carbon fiber, a heating composite material manufactured by the manufacturing method, a molded body including the heating composite material, and a heating product including the molded body.
  • the heating product-related market can be applied to any product that generates heat such as heating elements for building heating, saunas and steam generators, drying agricultural and marine products, and industrial heating elements. For this reason, the use of heating sheets is on the rise.
  • Heat-generating composite materials are plate-type, assembly-type, film, and sheet, and can be used in various household products such as electronic products, heating products, household products, medical supplies, beauty products, and functional clothing that require a constant temperature. This product is mainly used for industrial thermostats.
  • Heating composite materials are expanding the range of planar heating elements in the building heating field, and their application range is gradually expanding due to their high calorific value compared to the existing linear heating elements and quick heating control.
  • metal heating wires and ITO nanoparticle heating elements are mainly applied at present, but the scope of application is limited due to the heating element structure, high process cost, and temperature restrictions.
  • heating composite materials have the advantage of having sufficient competitiveness compared to other heating elements because they can be applied to various substrates through an inexpensive coating method. have.
  • planar heating elements are partially used for heating products due to the limitation of low-temperature heating temperature, and are forming a domestic market of 20 billion won per year.
  • Heating composite material is manufactured by extruding into a film shape in a state where the material is manufactured to maintain a constant electrical resistance through proper mixing and dispersion using nichrome wire, carbon fiber, carbon nanotube (CNT), ceramic powder, etc. on an existing metal plate.
  • nichrome wire, carbon fiber, carbon nanotube (CNT), ceramic powder, etc. on an existing metal plate.
  • it is manufactured by bonding it in various ways and applying electricity at a certain distance to generate heat.
  • a method of manufacturing a heating film having a multilayer by additionally adhering different materials is mainly used.
  • the present invention is to solve the necessity of the prior art as described above, and an object of the present invention is to provide a heating composite material manufactured by impregnating a metal-plated carbon fiber bundle with a resin and a method for manufacturing the same.
  • the present invention provides a method of manufacturing a heat-generating composite material using a metal-coated carbon fiber, comprising the following steps.
  • step S2 Passing the bundle of carbon fibers prepared in step S1 through a resin impregnation tank to prepare a resin-impregnated metal-coated carbon fiber (S2);
  • step S4 The carbon fiber dried in step S4 is cut to a predetermined length and pelletized to produce a heating composite material (S5).
  • the step S1 is,
  • Electrolytic plating of the carbon fiber electroless-plated in step S1-1 with a second metal (S1-2) may be included.
  • the bundle of carbon fibers in step S2 may include 100 to 50,000 monofilaments.
  • the impregnation in step S2 may be performed in a resin impregnation tank in which the resin is extruded at a pressure of 0.5 to 10 kg/cm 2 .
  • the resin is polyamide (PA), polyethylene (PE), polypropylene (PP), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyvinyl chloride (PVC) , polyvinyl alcohol (PVA), polystyrene (PS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), acrylonitrile-styrene copolymer resin (SAN), At least one thermoplastic resin selected from the group consisting of acrylonitrile-styrene-acrylate copolymer resin (ASA), polyphenylene ether (PPE), polyphenylene sulfide (PPS), and polyether ether ketone (PEEK) may be
  • the heating composite material may include 5 to 40% by weight of metal-coated carbon fiber and 60 to 95% by weight of a resin.
  • the drying in step S4 may be performed through air pressure applied at a pressure of 1 to 10 kg/cm 2 or hot air at 100° C. to 150° C.
  • the pelletization of step S5 may be cutting the dried carbon fibers to a length of 1 to 15 mm.
  • the resin may further include one or more materials selected from the group consisting of metal, carbon nanotubes, and graphene.
  • the present invention provides a heating composite material manufactured by the above manufacturing method.
  • the molded body and an electrode, which provides a heating product.
  • the present invention relates to a method for manufacturing a heating composite material comprising a metal-coated carbon fiber impregnated with a resin, a molded body manufactured through the heating composite material, and a heating product including the molded body, according to the manufacturing method of the present invention , the metal-coated carbon fiber inside the heating composite material is included in a certain arrangement and a certain length, so that the electrical resistance of the heating composite material can be easily controlled.
  • the exothermic composite material of the present invention can be easily commercialized by a molding method through a general injection method, a complex shape can be easily commercialized in one process. It has the advantage of easy product manufacturing.
  • FIG. 1 is a diagram schematically illustrating a method for manufacturing a heating composite material of the present invention, a method for manufacturing a molded body using the heating composite material, and a method for manufacturing a heating product using the molded body.
  • FIG. 2 is a schematic view showing a manufacturing apparatus for manufacturing a heating composite material of the present invention.
  • FIG 3 is a view showing a cross-section of the heating composite material of the present invention.
  • FIG. 4 is a view showing a test piece for measuring the amount of heat generated by connecting an electrode to the molded article of the present invention.
  • FIG. 5 is a result of measuring the heating temperature generated by changing the amount of power input to the test piece of the present invention
  • FIG. 5a is a thermal image result measured by inputting power to 0.5V, 0.89A
  • FIG. 5C is a thermal image result measured by supplying power to 1.5V and 2.6A
  • FIG. 5D is a thermal image measured by supplying electric power to 2.0V and 3.41A
  • Figure 5e is a thermal image result measured by applying power to 2.5V, 3.92A
  • Figure 5f is a thermal image result measured by inputting power to 3.0V, 4.36A
  • Figure 5g is 3.5V
  • 4.63 It is a diagram showing the thermal image result measured by supplying power to A.
  • the present invention is a result of intensive research to produce a heat-generating composite material that is easy to commercialize and has excellent heat-generating performance.
  • a resin is impregnated into a bundle-type metal-coated carbon fiber to produce a pellet-type heat-generating composite material, heat generation performance and a heat-generating composite material having excellent physical properties, and confirmed that it can be easily manufactured into a heat-generating product through the heat-generating composite material, thereby completing the present invention.
  • 1 schematically shows a method for manufacturing a heating composite material of the present invention, injection molding the heating composite material, and printing and assembling electrodes to produce a heating product.
  • the present invention provides a method for manufacturing a heat-generating composite material using a metal-coated carbon fiber, comprising the following steps:
  • step S2 Passing the bundle of carbon fibers prepared in step S1 through a resin impregnation tank to prepare a resin-impregnated metal-coated carbon fiber (S2);
  • step S4 The carbon fiber dried in step S4 is cut to a predetermined length and pelletized to produce a heating composite material (S5).
  • the present invention relates to a method of manufacturing a heat-generating composite material manufactured by pressurizing and impregnating a thermoplastic resin between fiber bundles using a metal coated carbon fiber (MCF), as schematically shown in FIG. 2 .
  • MCF metal coated carbon fiber
  • the metal-coated carbon fiber used in the present invention can be used without limitation as long as it is a carbon fiber coated with a metal through a plating process on the outer diameter of the carbon fiber. And it is preferable to use a carbon fiber coated with a metal doubly through electrolytic plating.
  • the step S1 includes: electroless plating the carbon fiber with a first metal (S1-1); and electrolytically plating the carbon fiber electroless-plated in step S1-1 with a second metal (S1-2).
  • the types of the first metal and the second metal may be the same or different from each other, and preferably, the first metal may be nickel or copper, and the second metal may be nickel.
  • the electroless and electrolytic process of the present invention may be performed through the method disclosed in Korean Patent No. 1427309, but is not limited thereto.
  • the step S1-1 may be plated by passing carbon fibers through an electroless plating solution containing pure water, a first metal salt, a complexing agent, a reducing agent, a stabilizer and a pH adjusting agent, and the S1-2 step is S1 It is performed continuously following step -1 and may be performed by applying a constant voltage (CV) of 5-15 Volts using a second metal salt and a pH buffer, but is not limited to the above method.
  • CV constant voltage
  • step S1-1 and step S1-2 (1) passing the carbon fiber through an aqueous solution containing a surfactant, an organic solvent and a nonionic surfactant to degrease and soften the carbon fiber; (2) the carbon fiber resulting from the step (1) sodium bisulfite (NaHSO 3 ), sulfuric acid (H 2 SO 4 ), ammonium persulfate (ammonium persulfate; (NH 4 ) 2 S 2 O 8 ) and performing an etching process for neutralization, cleaning and conditioning by passing through an aqueous solution containing pure water; (3) passing the carbon fiber resulting from the step (2) through an aqueous solution of PdCl 2 to perform a sensitizing process; and (4) passing the carbon fiber resulting from step (3) through an aqueous solution of sulfuric acid (H 2 SO 4 ) to perform an activating process.
  • Fibers may be used, but are not limited thereto.
  • the thickness of the metal coating produced by the plating may be 50 to 500 nm.
  • the electrical resistance of the metal-coated carbon fiber may be different depending on the thickness of the metal coating, and the preferable electrical resistance may be 0.1 to 10 ⁇ /m, but is not limited thereto.
  • the carbon fiber is characterized in that it is in the form of a bundle.
  • the bundle of carbon fibers includes 100 to 50,000 monofilaments, preferably 1K (1,000 monofilaments), 3K (3,000 monofilaments), 6K (6,000 monofilaments), 12K (12,000 monofilaments). ), a bundle of carbon fibers of 48K (48,000 monofilaments) can be used, and more preferably, a bundle of carbon fibers of 8K (8,000 monofilaments) to 16K (16,000 monofilaments) can be used, and the present invention A 12K carbon fiber bundle may be used as in the embodiment.
  • the metal-coated carbon fiber may be provided in the form of being wound on a bobbin, and transferred to the resin impregnation tank through a fiber guide roller.
  • the fiber guide roller is used to minimize frictional force to reduce peeling of the metal coating layer, and the guide roller may be further provided between the resin impregnation tank and the cooling unit where the resin is cured, as shown in FIG. 2 .
  • Step S2 of the present invention is a step of impregnating the resin in the bundle of carbon fibers.
  • the impregnation may be performed in a resin impregnation tank in which the resin is extruded at a pressure of 0.5 to 10 kg/cm 2 .
  • the resin is a thermoplastic resin, polyamide resin (PA6, PA66, etc.), polyethylene (PE), polypropylene (PP), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polyvinyl chloride (PVC), Polyvinyl alcohol (PVA), polystyrene (PS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), acrylonitrile-styrene copolymer resin (SAN), acrylic Ronitrile-styrene-acrylate copolymer resin (ASA), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), and the like may be used.
  • PA6 PA66, etc. polyamide resin
  • PE polyethylene
  • PP polypropylene
  • ABS acrylonitrile butadiene styrene
  • PC polycarbonate
  • the polyamide has a density of 1.14 g/cm 3 , a melting point of 220 to 255° C., a tensile strength of 83 to 85 MPa, an Izod impact strength of 7.0 to 7.5Kg f ⁇ cm/cm, and a heat deflection temperature of 65 to 85° C. it's not going to be
  • the resin is melted by heating within the range of 100 to 500°C in consideration of the melting point and extruded into the resin impregnation tank through a resin extruder.
  • the resin impregnation amount is adjusted in consideration of the cross-sectional area of the fiber, and the pressure can be adjusted by adjusting the diameter size of the resin extruder.
  • the pressure is more preferably 1 to 3 kg/cm 2 in terms of the cross-sectional area of the bundle of carbon fibers used.
  • the exothermic composite material of the present invention may include 5 to 40% by weight of metal-coated carbon fiber and 60 to 95% by weight of a resin. More preferably, when 25 to 35% by weight of the metal-coated carbon fiber and 75 to 65% by weight of the resin are included, it may be made of a heating composite material having desirable heating performance for use in heating products.
  • the drying in step S4 may be performed by air pressure applied at a pressure of 1 to 10 kg/cm 2 or hot air at 100° C. to 150° C., but the drying method is the type of resin used and the process is performed. It can be freely selected and performed according to the environment and the like.
  • the carbon fiber may be transferred to a pelletizer through a drawing device.
  • the drawing device is a roller-type device that pulls the material in which the fiber and the impregnated resin are combined, and a urethane or rubber roller with high frictional force may be used.
  • the pelletization of step S5 may be performed by cutting the dried carbon fibers to a length of 1 to 15 mm. More preferably, it may be provided in a length of 4 mm to 8 mm, which is a size that is easy to be put into a mold when injection molded.
  • the resin of the present invention may further include one or more materials selected from the group consisting of metals, carbon nanotubes, and graphene according to the characteristics of the heat generating product to be manufactured.
  • the type of the metal is not limited.
  • the present invention provides a heating composite material manufactured by the above manufacturing method.
  • the pelletized heating composite material may be melted and then injected into a mold to be molded into a desired shape to produce a molded body.
  • the molded body may be mixed with different types of pellets to control the color of the product, the flowability of the liquid, and the dispersibility of the fibers.
  • the power input unit can be designed/manufactured, and the design/manufacturing method can be freely selected according to the type, shape, and environment of the heating product to be manufactured. can be designed/manufactured.
  • the electrode is a conductive material, and may be at least one selected from the group consisting of copper, silver (Ag), gold (Au), carbon nanotubes (CNT), and graphene.
  • metal-coated carbon fiber (MCF) was manufactured by the metal-plated carbon fiber manufacturing method according to Patent No. 1427309. By making the metal coating thicknesses different from each other, Sample-1 to Sample-4 shown in Table 1 were prepared.
  • Fiber specific gravity fiber electrical resistance 100 nm 2.13 4 Sample-2 130 nm 2.24 3 Sample-3 190 nm 2.45 2 Sample-4 360 nm 3.0
  • Resins shown in Table 2 below were prepared as resins impregnated into metal-coated carbon fibers.
  • PA6 was selected and used among the resins.
  • the 12,000 strands of MCF fiber of Sample-3 were uniformly impregnated with PA6 resin to make the composite material linear, and the composite material was cut to a length of 6 mm to prepare pellets.
  • the pellets have a resin impregnated between fiber bundles.
  • Example 1 By melting the pellets of Example 1 in an injection molding machine, a plate product (size: 6 mm (T) x 12 mm (W) x 100 mm, volume: 7.2 cm 3 ) was produced.
  • the electrical resistance according to the amount of the resin impregnated was measured, and is shown in Table 3 below.
  • Sample MCF PA 6 electrical resistance ⁇ /cm 3 One 10% 90% 100 to 200 2 20% 80 50 to 100 3 30% 70 15 to 40 4 40% 60 5 to 10
  • Example 3 in order to manufacture a heating product connected to an electrode, a pellet containing 30 wt% of MCF fiber and 70 wt% of a resin is melted and put into a mold, 16 mm (T) x 12 mm (W) x 100 mm to prepare a test piece.
  • copper wires were heat-sealed and inserted at both ends to fabricate the power input part on the manufactured test piece, thereby manufacturing the power input part.
  • a DC power supply device was connected to the test piece, and the exothermic temperature was measured with a thermal imaging camera 10 seconds after power input, as shown in FIGS. 5A to 5G .

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  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un matériau de chauffage composite au moyen de fibres de carbone revêtues de métal, un matériau de chauffage composite préparé par le procédé, un corps moulé comprenant le matériau de chauffage composite et un produit de génération de chaleur comprenant le corps moulé. Le matériau de chauffage composite selon la présente invention est préparé par l'imprégnation d'une résine dans un faisceau de fibres de carbone revêtues de métal et présente d'excellentes performances de génération de chaleur.
PCT/KR2021/005853 2020-05-11 2021-05-11 Procédé de préparation de matériau de chauffage composite au moyen de fibres de carbone revêtues de métal et matériau de chauffage composite préparé par ledit procédé WO2021230608A1 (fr)

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KR1020200055920A KR102231216B1 (ko) 2020-05-11 2020-05-11 금속코팅 탄소섬유를 이용한 발열복합소재의 제조방법 및 상기 제조방법에 의한 발열복합소재
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KR20120129297A (ko) * 2011-05-19 2012-11-28 삼성전자주식회사 발열 복합체, 및 이를 포함하는 가열장치와 정착장치
KR101427309B1 (ko) * 2013-03-25 2014-08-06 주식회사 불스원신소재 무전해 및 전해 도금의 연속 공정을 이용한 고전도성 탄소 섬유의 제조 방법
JP2017057246A (ja) * 2015-09-14 2017-03-23 リンテック株式会社 柔軟性シート、熱伝導部材、導電性部材、帯電防止部材、発熱体、電磁波遮蔽体、及び柔軟性シートの製造方法
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KR20190057008A (ko) * 2017-11-17 2019-05-27 김성호 탄소 섬유를 이용한 복사열이 강한 온열 시트
KR101963256B1 (ko) * 2018-10-19 2019-03-29 (주)비에스엠신소재 금속 도금된 탄소 섬유를 이용한 발열 필름의 제조 방법
KR102231216B1 (ko) * 2020-05-11 2021-03-23 (주)비에스엠신소재 금속코팅 탄소섬유를 이용한 발열복합소재의 제조방법 및 상기 제조방법에 의한 발열복합소재

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