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WO2022220340A1 - Procédé de fabrication d'un matériau composite polymère translucide, et matériau composite polymère translucide fabriqué par celui-ci - Google Patents

Procédé de fabrication d'un matériau composite polymère translucide, et matériau composite polymère translucide fabriqué par celui-ci Download PDF

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Publication number
WO2022220340A1
WO2022220340A1 PCT/KR2021/009825 KR2021009825W WO2022220340A1 WO 2022220340 A1 WO2022220340 A1 WO 2022220340A1 KR 2021009825 W KR2021009825 W KR 2021009825W WO 2022220340 A1 WO2022220340 A1 WO 2022220340A1
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Prior art keywords
composite material
polymer composite
carbon
conductive polymer
translucent conductive
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PCT/KR2021/009825
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English (en)
Korean (ko)
Inventor
이민욱
황지영
김희진
박상유
양철민
강승범
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Korea Carbon Industry Promotion Agency
Korea Institute of Science and Technology KIST
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Korea Carbon Industry Promotion Agency
Korea Institute of Science and Technology KIST
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Publication of WO2022220340A1 publication Critical patent/WO2022220340A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/38—Removing material by boring or cutting
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced

Definitions

  • the present invention relates to a method for producing a translucent conductive polymer composite material having translucency, high conductivity, and exothermic properties, and to a translucent conductive polymer composite material manufactured thereby.
  • Carbon nanotubes were discovered by a Japanese scientist in 1991, and it took 20 years to mass-produce and apply a material with electrical properties higher than copper, thermal properties higher than diamond, and mechanical properties thousands of times that of steel. It has become an abnormality, and foreign substances are being applied as additives to various substances.
  • Carbon nanotubes mainly use materials containing carbon nanotubes, and development of materials having functions such as tensile strength, antistatic properties, conductivity, thermal conductivity, far-infrared emission and electromagnetic wave shielding is being actively conducted.
  • materials having functions such as tensile strength, antistatic properties, conductivity, thermal conductivity, far-infrared emission and electromagnetic wave shielding
  • a polymer such as polyamide, polyester, polyether or polyimide, silicone, rubber, or an inorganic material such as glass or ceramic material
  • an inorganic material such as glass or ceramic material
  • carbon-based materials have been widely used as materials for heating elements, but carbon-based materials are opaque materials and have a disadvantage in that they are difficult to apply to windows of houses or automobiles, or parts that require transparency of displays or touch panel elements.
  • carbon-based composite materials are opaque and have a problem in that their properties change when they have transparency.
  • bromobutyl rubber As one of the rubber-based polymers, bromobutyl rubber (BIIR) has characteristics such as high tensile strength, vibration reduction, low permeability, and high resistance to aging and weathering. The reality is that the technology and application method for stably dispersing in the polymer matrix are lacking, so it cannot be applied in more various fields.
  • the present invention provides a method for producing a semi-transparent conductive polymer composite material having excellent translucency and heat generation property by forming uniform holes using a laser in order to solve the transparency limitation of the conventional carbon material, and a semi-transparent conductive polymer composite material manufactured according to the method To provide a transparent conductive polymer composite material.
  • the present invention in one embodiment, (A) mixing bromobutyl rubber (BIIR) and hexane; (B) after mixing the carbon-based filler and isopropyl alcohol, sonicating by adding a dimethyl silicone oil (MEP) solution; (C) adding the mixture mixed in step (A) to the mixture mixed in step (B) and stirring; (D) hardening by injecting the mixture mixed in step (C) into a hot press; And, (E) provides a method for producing a translucent conductive polymer composite material comprising the step of forming a plurality of holes using a laser after the curing.
  • BIIR bromobutyl rubber
  • MEP dimethyl silicone oil
  • bromobutyl rubber may be mixed in a composition ratio of 1 to 10 w/v%.
  • step (B) the carbon-based filler and isopropyl alcohol may be mixed in a weight ratio of 1:50 to 1:500.
  • the content of the carbon-based filler in step (B) may be 1 to 35 wt%.
  • the step (C) may further include the step of additionally adding hexane so that the volume ratio of hexane and isopropyl alcohol to the mixture mixed in step (C) becomes 5:1 to 1:1.
  • the holes may be uniformly formed in a side-by-side arrangement or a staggered arrangement.
  • the carbon-based filler may be one selected from the group consisting of carbon nanotubes (CNT), graphene, artificial graphite, activated carbon, carbon black, and carbon fibers.
  • CNT carbon nanotubes
  • graphene graphene
  • artificial graphite artificial graphite
  • activated carbon carbon black
  • carbon fibers carbon fibers
  • the present invention provides a translucent conductive polymer composite material manufactured according to the method for manufacturing the translucent conductive polymer composite material.
  • the semi-transparent conductive polymer composite material prepared according to the method for producing a semi-transparent conductive polymer composite material of the present invention has high conductivity, which is an excellent property of both carbon-based fillers (especially carbon nanotubes) and bromobutyl rubber (BIIR). And it is possible to solve the limitations of transparency of the conventional carbon material by producing a translucent composite material having high conductivity and heat-generating properties as it is by forming uniform holes and having exothermic properties.
  • the translucent conductive polymer composite material according to the present invention can be attached or used as a curtain, which has visibility to see the outside landscape, can block the view from the outside, and serves as a planar heating element in winter for the purpose of cold protection can be used as
  • FIG. 1 is a flowchart showing a method of manufacturing a translucent conductive polymer composite material according to the present invention.
  • FIG. 2 is a schematic view showing the arrangement of holes in the translucent conductive polymer composite material according to the present invention.
  • Example 6 is a graph showing the exothermic temperature and exothermic cycle characteristics of the specimens prepared according to Comparative Example 1 and Example 1 in the present invention [(a) Comparative Example 1, (b) Example 1, (c) Comparison Example 1 vs Example 1].
  • FIG. 8 is a photograph taken according to the focal point by installing the translucent conductive polymer composite material according to the present invention on a window.
  • the present invention relates to a method for manufacturing a translucent composite material having high conductivity and heat-generating properties as it is by forming a hole in a carbon-based rubber composite material, and to a translucent conductive polymer composite material manufactured according to the method.
  • the present invention comprises the steps of (A) mixing bromobutyl rubber (BIIR) and hexane; (B) after mixing the carbon-based filler and isopropyl alcohol, sonicating by adding a dimethyl silicone oil (MEP) solution; (C) adding the mixture mixed in step (A) to the mixture mixed in step (B) and stirring; (D) hardening by injecting the mixture mixed in step (C) into a hot press; And, (E) provides a method for producing a translucent conductive polymer composite material comprising the step of forming a plurality of holes using a laser after the curing.
  • BIIR bromobutyl rubber
  • MEP dimethyl silicone oil
  • bromobutyl rubber hexane
  • carbon nanotube CNT
  • carbon black carbon black
  • metal fiber isopropyl alcohol and dimethyl silicone oil (MEP)
  • BIIR bromobutyl rubber
  • CNT carbon nanotube
  • MEP dimethyl silicone oil
  • FIG. 1 is a schematic view showing a method of manufacturing a translucent conductive polymer composite material according to the present invention.
  • the method for producing a translucent conductive polymer composite material comprises the steps of (A) mixing bromobutyl rubber (BIIR) and hexane; (B) after mixing the carbon-based filler and isopropyl alcohol, sonicating by adding a dimethyl silicone oil (MEP) solution; (C) adding the mixture mixed in step (A) to the mixture mixed in step (B) and stirring; (D) hardening by injecting the mixture mixed in step (C) into a hot press; and (E) forming a plurality of holes using a laser after the curing.
  • BIIR bromobutyl rubber
  • MEP dimethyl silicone oil
  • step (A) bromobutyl rubber (BIIR) is added to hexane and mixed by stirring.
  • BIIR bromobutyl rubber
  • the bromobutyl rubber is one of the polymers with excellent flexibility, elasticity, chemical stability and solubility, and in particular, has excellent self-healing properties and is used as a material for filling cracks or irregular holes in tires or ships.
  • the hexane is one of the non-polar solvents and is used as a solvent for uniformly dispersing the bromobutyl rubber (BIIR).
  • bromobutyl rubber may be mixed in a composition ratio of 1 to 10 w/v%, preferably in a composition ratio of 4 w/v%.
  • the dispersion degree of bromobutyl rubber (BIIR) in hexane is high and handling is easy, so that bromobutyl rubber (BIIR) can be more effectively dispersed uniformly.
  • step (B) the carbon-based filler and isopropyl alcohol may be mixed and sonicated, and then dimethyl silicone oil (MEP) may be added and mixed.
  • MEP dimethyl silicone oil
  • the carbon-based filler After mixing the carbon-based filler with isopropyl alcohol, it is treated with ultrasonic waves for 10 to 60 minutes, preferably for 30 minutes.
  • the carbon-based filler may be one selected from the group consisting of carbon nanotubes (CNT), graphene, artificial graphite, activated carbon, carbon black, and carbon fibers.
  • CNT carbon nanotubes
  • the dried carbon-based filler tends to agglomerate strongly, which is caused by van der Waals force to form bundles and aggregate, thereby minimizing surface energy by minimizing interfacial contact with the solvent. is the action to do.
  • the agglomerated carbon-based filler in order to disperse the agglomerated carbon-based filler, is mixed with isopropyl alcohol and then sonicated to disperse the carbon-based filler.
  • isopropyl alcohol Since the solvent mixed with the carbon-based filler should be evaporated without leaving air for excellent conductivity when the solvent is evaporated later, it is preferable to use isopropyl alcohol.
  • the isopropyl alcohol has a stable structure composed of three carbons and one oxygen, so that a material having a hydrophobic part or a hydrophilic part easily contacts the surface of the carbon-based filler.
  • the carbon-based filler partially dissolved in isopropyl alcohol is completely mixed through ultrasonic waves.
  • the ultrasonic treatment breaks the van der Waals force between the mutual surfaces of the aggregated carbon-based filler bundle by applying a physical force, and separates the carbon-based filler into a single carbon-based filler.
  • the ultrasonic treatment method is a bath sonication method in which the ultrasonic treatment is performed while maintaining the temperature below room temperature, preferably 10 to 23 ° C. within a time of 10 to 60 minutes to minimize damage to the carbon-based filler as well as to stabilize the dispersion.
  • the ultrasonic wave intensity (spatial peak pulse average intensity: ISPPA) in the frequency range of about 40 to 5,000 kHz by using ultrasonic waves that vary between about 50 to 1,000 mW, it is possible to obtain a stable dispersion in which the carbon-based filler is evenly dispersed.
  • ISPPA spatial peak pulse average intensity
  • the carbon-based filler cannot be completely separated and stably dispersed in the solvent, so isopropyl alcohol and ultrasonication are performed together It is preferable to do
  • the carbon-based filler and isopropyl alcohol are mixed in a weight ratio of 1:50 to 1:500, preferably 1:95 to 1:450 by weight.
  • the weight ratio of isopropyl alcohol based on the carbon-based filler is out of the above range, the aggregated carbon-based filler may not be separated and the separated carbon-based filler may not be stably dispersed in isopropyl alcohol.
  • the carbon-based filler is carbon nanotube (CNT)
  • the content of carbon nanotube (CNT) in the mixture is 1 to 35 wt%, preferably 5 to 20 wt%. It is possible to prepare a self-healing conductive rubber composite material in which carbon nanotubes (CNTs) are uniformly dispersed within the above range, and maintain properties such as excellent electrical conductivity, thermal conductivity and elasticity of carbon nanotubes (CNTs).
  • the ultrasonic treatment is performed under the same conditions as the ultrasonic treatment performed on the carbon-based filler and isopropyl alcohol, but for 5 to 20 minutes, preferably 10 to 15 minutes. If the ultrasonic treatment time is less than the lower limit, dimethyl silicone oil (MEP) cannot wrap the carbon-based filler, and if it exceeds the upper limit, it may rather prevent the dimethyl silicone oil (MEP) from wrapping the carbon-based filler, and in the future Immiscible with bromobutyl rubber (BIIR).
  • MEP dimethyl silicone oil
  • BIIR bromobutyl rubber
  • the dimethyl silicone oil (MEP) comes into contact with the hydrophobic part of isopropyl alcohol, and surrounds the dispersed carbon-based filler by ultrasonication.
  • the viscosity of the dimethyl silicone oil (MEP) is 70 to 200 cSt, preferably 100 to 150 cSt, and when the viscosity is less than the lower limit, the carbon-based filler cannot be wrapped, and when it exceeds the upper limit, the carbon-based filler is added to the solution It can be difficult to disperse within.
  • the dimethyl silicone oil (MEP) solution is a dimethyl silicone oil (MEP) solution having a concentration of 0.1 to 1%, preferably 0.2 to 0.5%.
  • concentration of the dimethyl silicone oil (MEP) solution is less than the lower limit, the carbon-based filler cannot be wrapped, and when it exceeds the upper limit, a more stable dispersion cannot be obtained.
  • step (C) the mixture mixed in step (A) is added to the mixture mixed in step (B) and stirred.
  • step (C) stir the mixture mixed in step (C) at 500 to 1,500 rpm for 30 minutes so that excess hexane and isopropyl alcohol are first mixed and bromobutyl rubber (BIIR) is completely dissolved in the carbon-based filler solution.
  • BIIR bromobutyl rubber
  • the mixture mixed in step (C) may be injected into a hot press and then cured.
  • the mixture mixed in step (C) may be injected into a hot press, which is a molding die, and then cured at 120° C. and 4,000 psi for 10 minutes.
  • the translucent conductive polymer composite material according to the present invention can be attached to a window or used as a curtain, and a planar heating element in winter It can be used for cold weather purposes.
  • step (C) the step of evaporating the solvent present in the mixture mixed in step (B) may be further included.
  • step (E) a plurality of holes may be formed in the cured composite material using a laser. By forming the hole, a translucent conductive polymer composite material can be manufactured.
  • the laser may be using a CO 2 laser cutting system.
  • the size (diameter) of the holes may be 0.5 to 2 mm, preferably 1 mm, and the spacing between the holes may be 0.5 to 2 mm, preferably 1 mm.
  • the holes may be uniformly formed in a side-by-side arrangement or a staggered arrangement.
  • FIG. 2 is a schematic view showing the arrangement of holes in the translucent conductive polymer composite material.
  • holes are formed in the same column in all rows, and in a staggered arrangement, holes are formed by alternating rows between rows.
  • the holes may have similar tensile strength according to the side-by-side arrangement or the staggered arrangement, but in the case of the staggered arrangement, the tensile strain may be greater than that of the side-by-side arrangement of the composite material.
  • the translucent conductive polymer composite material is manufactured in a solution method, so it is easy to handle. It has a low cost effect.
  • the semi-transparent conductive polymer composite material prepared according to the method for producing the semi-transparent conductive polymer composite material of the present invention has excellent properties of high conductivity and By producing a translucent composite material that has exothermic properties and uniform holes to form high conductivity and heat-generating properties as it is, it is possible to solve the limitations of transparency of conventional carbon materials.
  • the present invention provides a translucent conductive polymer composite material manufactured according to the method for manufacturing the translucent conductive polymer composite material.
  • the translucent conductive polymer composite material according to the present invention can be attached or used as a curtain, which has visibility to see the outside landscape, can block the view from the outside, and is used as a planar heating element in winter for cold protection purposes This is possible.
  • Example 1 Preparation of Translucent Conductive Polymer Composite Material Containing 5% by Weight of CNTs (Forming Holes in Staggered Arrangement)
  • a 4% (w/v) solution of bromobutyl rubber (BIIR) in hexane was prepared. Then, 5% (w / w) of carbon nanotubes (CNT) was added to isopropyl alcohol to disperse, and 4% (w / w) of dimethyl silicone oil (MEP) solution was added to the carbon nanotube (CNT) solution. added and sonicated. Then, the bromobutyl rubber (BIIR) solution was slowly added to the carbon nanotube (CNT) solution and mixed at the maximum speed for 30 minutes.
  • BIIR bromobutyl rubber
  • a translucent conductive polymer composite material was prepared by forming a plurality of holes in a staggered arrangement using a laser (CO 2 laser cutting system, hole diameter 1 mm, spacing 1 mm) in the cured composite material.
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 1, except that 10% (w/w) carbon nanotube (CNT) was used.
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 1, except that 15% (w/w) carbon nanotube (CNT) was used.
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 1, except that 20% (w/w) carbon nanotube (CNT) was used.
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 1, except that a plurality of holes were formed in a side by side arrangement in the cured composite material using a laser.
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 5, except that 10% (w/w) carbon nanotube (CNT) was used.
  • Example 7 Preparation of Translucent Conductive Polymer Composite Material Containing 15% by Weight of CNTs (Positioning Holes in Side by Side Arrangement)
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 5, except that 15% (w/w) carbon nanotube (CNT) was used.
  • Example 8 Preparation of Translucent Conductive Polymer Composite Material Containing 20% by Weight of CNTs (Positioning Holes in Side by Side Arrangement)
  • a translucent conductive polymer composite material was prepared in the same manner as in Example 5, except that 20% (w/w) carbon nanotubes (CNT) were used.
  • Comparative Example 1 Preparation of a conductive polymer composite material without pores containing 5 wt% of CNT
  • Comparative Example 2 Preparation of non-porous conductive polymer composite material containing 10% by weight of CNT
  • Comparative Example 3 Preparation of non-porous conductive polymer composite material containing 15% by weight of CNT
  • Comparative Example 4 Preparation of a conductive polymer composite material without pores containing 20 wt% of CNT
  • Table 1 below is a table showing the surface resistance and electrical conductivity of the carbon-based conductive polymer composite materials prepared according to Comparative Examples 1 to 4, respectively (in the case of Examples, it is difficult to measure the surface resistance due to holes).
  • the specimens according to Examples 1 to 5 were tested at a size of 20 ⁇ 50 mm and a head speed of 500 mm/min.
  • Figure 3 shows the results of tensile strength and tensile strain (Tensile strain) measurement according to the hole arrangement according to Examples 1 and 5 and photographs of the specimen after the tensile test.
  • Heating condition After cutting Comparative Examples 1 and 1 to a size of 150 ⁇ 210 mm 2 and attaching conductive copper tape to both ends to connect them, a voltage of 20 to 58V and a current of 0.34 to 0.91A were supplied with a DC power supply. It was heated at 10-50W of power.
  • Temperature change measurement An infrared thermal image was taken using a FLIR IR camera to measure temperature change.
  • Heating rate measurement The heating rate of Comparative Example 1 and Example 1 was measured at an average of 40W by supplying an average voltage of 50V and an average current of 0.8A as a DC power supply, and the measurement environment was an average of 25°C, 42-48% relative humidity. was measured in
  • Example 5 is an image showing photographs and exothermic characteristics of specimens prepared according to Comparative Example 1 and Example 1.
  • FIG. It was confirmed that the translucency was exhibited in Example 1 with uniform interlacing holes as compared with Comparative Example 1 without holes, and it was confirmed that the highest heating temperature was higher and the heating uniformity was also better.
  • FIG. 6 is a graph comparing the heating rate while heating the specimens prepared according to Comparative Example 1 and Example 1 at 10 to 50 W, respectively [control is Comparative Example 1, ST (semi transparency) is Example 1, at this time One heating temperature is within a 150 ⁇ 150 mm box. average exothermic temperature].
  • ST sin transparency
  • One heating temperature is within a 150 ⁇ 150 mm box. average exothermic temperature.
  • the maximum heating temperature is higher and the heat generation rate and cooling rate are faster due to the uniform transfer of heat due to the uniform arrangement of the holes. could It was found that this was an ideal shape as a heating element.
  • Example 7 is a graph showing the exothermic rate and exothermic cycle at 40W of the specimens prepared according to Comparative Examples 1 and 1 [(a) Comparative Example 1, (b) Example 1, (c) Comparative Example 1 vs. Example 1 (control is Comparative Example 1, ST (semi transparency) is Example 1), at this time, the indicated exothermic temperature is within a 150 ⁇ 150 mm box average exothermic temperature]. This shows a high heating effect even at a low power of 40W, and the thermal stability according to the heating cycle was the same for both samples.
  • Translucency was confirmed by installing the translucent conductive polymer composite material prepared in Example 1 on a window.
  • FIG. 8 shows a photograph according to the focus of the translucent conductive polymer composite material installed on the window.
  • the translucent conductive polymer composite material according to the present invention has translucency in the photograph taken with the focus on the composite material and the photograph with the focus on the landscape.

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Abstract

La présente invention concerne un procédé de fabrication d'un matériau composite polymère conducteur translucide ayant des propriétés translucides, une conductivité élevée et des propriétés exothermiques, et un matériau composite polymère conducteur translucide fabriqué par celui-ci. Le matériau composite polymère conducteur translucide fabriqué conformément au procédé de fabrication d'un matériau composite polymère conducteur translucide selon la présente invention présente une conductivité élevée et des propriétés exothermiques qui sont d'excellentes propriétés d'une charge à base de carbone (en particulier un nanotube de carbone) et du caoutchouc bromobutyle (BIIR). De plus, il est possible de remédier aux limitations en termes de transparence d'un matériau composite de carbone conventionnel en fabricant un matériau composite translucide ayant une conductivité élevée et des propriétés exothermiques en formant des trous uniformes.
PCT/KR2021/009825 2021-04-13 2021-07-28 Procédé de fabrication d'un matériau composite polymère translucide, et matériau composite polymère translucide fabriqué par celui-ci Ceased WO2022220340A1 (fr)

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KR1020210047512A KR102420931B1 (ko) 2021-04-13 2021-04-13 반투명성 고분자 복합소재의 제조방법 및 이에 따라 제조된 반투명성 고분자 복합소재

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