WO2016063809A1 - 複合素材および強化繊維 - Google Patents
複合素材および強化繊維 Download PDFInfo
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- WO2016063809A1 WO2016063809A1 PCT/JP2015/079333 JP2015079333W WO2016063809A1 WO 2016063809 A1 WO2016063809 A1 WO 2016063809A1 JP 2015079333 W JP2015079333 W JP 2015079333W WO 2016063809 A1 WO2016063809 A1 WO 2016063809A1
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
Definitions
- the present invention relates to a composite material having carbon nanotubes (hereinafter referred to as “CNT”) attached to the fiber surface, and a reinforcing fiber using the same.
- CNT carbon nanotubes
- CNTs adhere uniformly to the fiber surface in order to exhibit the function as a composite material.
- fibers are put into a solution in which CNTs are dispersed at a nano level (in some cases, abbreviated as a CNT nano dispersion liquid), and after the CNTs adhere to the fiber surface, It is manufactured by pulling up fibers from the dispersion and drying.
- a CNT nano dispersion liquid in which CNTs are dispersed at a nano level
- the CNT nanodispersion is supplementarily subjected to ultrasonic irradiation or stirring (see Patent Document 1).
- the dispersant is necessary for dispersing the CNT, and is generally used as an essential component in the manufacturing process of the composite material.
- an adhesive agent and other additives are added to the CNT nanodispersion to adhere the CNT to the fiber surface.
- the composite material produced in this way is expected to improve not only the original function of the fiber, but also the electrical conductivity, thermal conductivity, mechanical strength, etc. derived from the CNT as a composite material due to the CNT adhering to the fiber. Is done.
- An object of the present invention is to provide a composite material and a reinforced fiber that can exhibit functions such as electrical conductivity, thermal conductivity, mechanical strength, and the like derived from CNTs while allowing the original function of the fiber to be expressed. .
- the composite material according to the present invention is a composite material comprising fibers and a plurality of carbon nanotubes provided on the fiber surface, wherein the plurality of carbon nanotubes are directly attached to the fiber surface. .
- the reinforcing fiber according to the present invention includes a composite material and a resin composition covering the surface of the composite material.
- the composite material and the reinforcing fiber can exhibit the functions inherent to the fiber, and at the same time, can exhibit functions such as CNT-derived electrical conductivity, thermal conductivity, and mechanical strength.
- FIG. 4A is a SEM photograph of the composite material according to the example, FIG. 4A is a first place, FIG. 4B is a second place, FIG. 4C is a third place, and FIG. 4D is a fourth place.
- FIG. 6A is the first place
- FIG. 6B is the second place
- FIG. 6C is the third place
- FIG. 6D is a photograph of the fourth place.
- FIG. 6A is the first place
- FIG. 6B is the second place
- FIG. 6C is the third place.
- FIG. 6D is a photograph of the fourth place.
- It is a schematic diagram which shows the measuring method of interface adhesive strength.
- FIG. 8A is a comparative example
- FIG. 8B is an Example.
- the composite material 1 includes fibers 3 and CNTs 5 provided on the surface of the fibers 3.
- the fiber 3 is not particularly limited, and can be formed of a carbon material, a resin material, a metal material, a ceramic material, or the like. In the case of this embodiment, carbon fiber is applied as the fiber 3. In addition, in this figure, although the fiber 3 is illustrated by single, you may bundle and use two or more.
- the fiber 3 is not particularly limited, but has a diameter of about 3 to 150 ⁇ m obtained by firing organic fibers derived from petroleum, coal, coal tar, etc., such as polyacrylonitrile, rayon and pitch, and organic fibers derived from wood and plant fibers. The carbon fiber can be illustrated.
- the CNTs 5 are evenly distributed over almost the entire surface of the fiber 3 and are directly attached to the surface without inclusions at the boundary with the surface of the fiber 3 (FIG. 2). That is, the CNT 5 is directly attached to the surface of the fiber 3 without a dispersant or adhesive agent such as a surfactant interposed between the surface of the fiber 3.
- adhesive refers to bonding by van der Waals force.
- CNT5 is locally unevenly distributed on the surface of the fiber 3. Due to this uneven distribution, the surface of the fiber 3 is exposed from the CNT 5. This “uneven distribution” merely indicates that the CNT 5 does not cover the entire surface of the fiber 3 uniformly, and does not indicate whether the dispersibility of the CNT 5 is good.
- connection includes physical connection (simple contact).
- direct contact or direct connection includes a state in which a plurality of CNTs 5 are integrally connected in addition to a state in which a plurality of CNTs 5 are simply in contact with each other without inclusions, It should not be construed as limiting.
- the length of the CNT 5 is preferably 0.1 to 50 ⁇ m. If the length of the CNTs 5 is 0.1 ⁇ m or more, the CNTs 5 are intertwined and directly connected. Further, when the length of the CNT 5 is 50 ⁇ m or less, it becomes easy to disperse evenly. On the other hand, if the length of the CNTs 5 is less than 0.1 ⁇ m, the CNTs 5 are less likely to be entangled with each other. Further, CNT5 tends to aggregate when the length exceeds 50 ⁇ m.
- CNT5 preferably has an average diameter of about 30 nm or less.
- the diameter of the CNT 5 is 30 nm or less, the CNT 5 is rich in flexibility and deforms along the curvature of the surface of the fiber 3, so that the CNT 5 can be more reliably attached to the surface of the fiber 3.
- the diameter of the CNT 5 exceeds 30 nm, the flexibility is lost, and the CNT 5 is difficult to be deformed along the surface of the fiber 3, so that it is difficult to adhere to the surface of the fiber 3.
- the diameter of the CNT 5 is an average diameter measured using a transmission electron microscope (TEM) photograph.
- the average diameter of CNT5 is more preferably about 20 nm or less.
- the CNT 5 is preferably attached to the surface of the fiber 3 at a concentration of 0.001 to 20 wt% with respect to the fiber 3.
- concentration in the said range concentration in the said range, the part which is not covered with CNT5 in the fiber 3 surface is formed. The portion not covered with the CNT 5 is not covered with an adhesive or the like, and the surface of the fiber 3 is exposed. Thereby, the function of the fiber 3 is not impaired by the CNT 5.
- the concentration of CNT 5 is more preferably 0.01 to 10 wt% with respect to the fiber 3.
- the composite material 1 can be manufactured by producing CNT5, then producing a dispersion containing the CNT5, and attaching the CNT5 to the surface of the fiber 3 using the dispersion.
- each process is demonstrated in order.
- CNT5 for example, a catalytic film made of aluminum or iron is formed on a silicon substrate by using a thermal CVD method as described in JP-A-2007-126111, and a catalytic metal for growing CNT5 is used. A product produced by making fine particles and bringing a hydrocarbon gas into contact with the catalyst metal in a heated atmosphere is used.
- CNT5 obtained by other manufacturing methods such as an arc discharge method and a laser evaporation method
- the CNT 5 manufactured in this manufacturing example has a high aspect ratio and linearity of a diameter of 30 nm or less and a length of several hundred ⁇ m to several mm.
- CNT5 does not ask
- Nano-dispersion refers to a state in which CNTs 5 are physically separated and are not entangled and dispersed in a solution, and the ratio of aggregates of two or more CNTs 5 gathered in a bundle is 10% or less. Means a state.
- the CNT5 produced as described above is put into a solvent, and mechanical energy such as compressive force, shear force, impact force, friction force, etc. is applied to achieve uniform dispersion of the CNT5.
- the mechanical energy can be applied by, for example, a stirrer, a ball mill, a jet mill, a homogenizer, an ultrasonic disperser, or the like.
- the solvent examples include alcohols such as water, ethanol, methanol, isopropyl alcohol, and organic solvents such as toluene, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), hexane, normal hexane, ethyl ether, xylene, methyl acetate, and ethyl acetate.
- alcohols such as water, ethanol, methanol, isopropyl alcohol
- organic solvents such as toluene, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), hexane, normal hexane, ethyl ether, xylene, methyl acetate, and ethyl acetate.
- THF tetrahydrofuran
- MEK methyl ethyl ketone
- hexane normal hexane
- CNT adhesion In a state where the fibers 3 are immersed in the dispersion liquid prepared as described above, the CNTs 5 are attached to the surface of the fibers 3 while applying mechanical energy to the dispersion liquid as described above.
- the composite material 1 can exhibit functions such as electrical conductivity, thermal conductivity, mechanical strength, and the like derived from CNTs, while allowing the original function of the fiber to be expressed.
- the tow prepreg includes a composite material bundle obtained by bundling a plurality of composite materials 1, for example, about several thousand to several tens of thousands, and the resin composition covering the surface of the composite material bundle.
- the tow prepreg according to this embodiment is obtained by removing a resin composition from a commercially available tow prepreg (with no CNTs attached) to obtain fibers, and attaching CNTs to the fiber surface to produce a composite material bundle, Can be produced by covering with a resin composition.
- a resin composition from a commercially available tow prepreg (with no CNTs attached) to obtain fibers, and attaching CNTs to the fiber surface to produce a composite material bundle, Can be produced by covering with a resin composition.
- the 3 includes a resin removal tank 11, a CNT adhesion tank 14, and a resin coating tank 20.
- the resin removing tank 11 contains an organic solvent such as methyl ethyl ketone as the resin removing agent 12.
- the dispersion liquid (16 in the figure) shown in the first embodiment is accommodated in the CNT adhesion tank 14.
- the resin coating tank 20 contains a resin composition 22 dissolved by heating.
- a commercially available tow prepreg 100 is wound around a guide roller disposed in the resin removal tank 11 and is run at a predetermined running speed. Thereby, the commercially available tow prepreg 100 is immersed in the resin remover 12, and the resin composition is removed. At this time, it is preferable to apply the mechanical energy.
- the tow prepreg 100 is frayed by mechanical energy, and the resin composition can be efficiently removed. In this way, the resin composition is removed, and a bundle of fibers (hereinafter referred to as “fiber bundle”) 102 having an exposed surface is obtained.
- the fiber bundle 102 is wound around a guide roller disposed in the CNT adhesion tank 14 and travels in the CNT adhesion tank 14 at a predetermined traveling speed. As a result, the fiber bundle 102 is immersed in the dispersion liquid 16. At this time, CNT adheres efficiently to the fiber surface by applying the mechanical energy. In this way, a composite material bundle 18 is obtained.
- the composite material bundle 18 is wound around a guide roller disposed in the resin coating tank 20 and travels in the resin coating tank 20 at a predetermined traveling speed. Thereby, the composite material bundle 18 is impregnated in the dissolved resin composition 22.
- the resin composition include epoxy resins, phenol resins, melamine resins, urea resins (urea resins), unsaturated polyester resins, alkyd resins, thermosetting polyimides, polyethylene, polypropylene, polystyrene, Thermoplastic resins such as acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methacrylic resin, vinyl chloride, engineering plastics such as polyamide, polyacetal, polyethylene terephthalate, ultra high molecular weight polyethylene, polycarbonate, polyphenylene sulfide, polyether ether ketone, liquid crystal Super engineering plastics such as polymers, polytetrafluoroethylene, polyetherimi
- the tow prepreg 24 the CNTs 5 directly attached to the fiber and the fiber surface are covered with the resin composition. Therefore, the tow prepreg 24 can improve the mechanical strength by being reinforced with the CNT having the resin composition directly attached to the fiber surface.
- the procedure for removing the resin composition from the commercially available tow prepreg (no CNT attached) 100 and attaching the CNT to the surface of the fiber 3 to produce the composite material bundle 18 has been described. Is not limited to this. That is, it goes without saying that the step of removing the resin composition can be omitted if the fiber is not covered with the resin composition.
- the reinforcing fiber is provided with a composite material bundle in which, for example, several thousand to several tens of thousands of composite materials are bundled.
- the present invention is not limited to this and is formed of one composite material. It is good to do.
- Example (sample) A composite material according to the example was manufactured according to the procedure shown in the manufacturing method.
- CNT MW-CNT (Multi-Walled Carbon Nanotubes) grown on a silicon substrate to a diameter of 10 to 15 nm and a length of 100 ⁇ m or more by a thermal CVD method was used.
- a 3: 1 mixed acid of sulfuric acid and nitric acid was used, followed by filtration and drying after washing.
- tow prepreg a tow prepreg (manufactured by Toray Industries, Inc., model number: T-700) in which 12,000 carbon fibers having a diameter of 7 ⁇ m were bundled was used.
- MEK was used as a resin remover.
- the dispersion used methyl ethyl ketone as a solvent.
- the concentration of CNT5 in the dispersion was 0.01 wt%.
- a thermosetting epoxy resin was used as the resin composition.
- the tow prepreg was immersed in a resin remover to remove the resin composition to obtain a fiber bundle.
- the traveling speed of the tow prepreg at this time was 1.5 m / min. Further, mechanical energy was applied to the resin remover by ultrasonic waves.
- FIGS. 4A to 4D are photographs taken at four different locations in the length direction of one composite material.
- FIG. 5 shows a SEM photograph of the fiber before adhering CNTs.
- FIGS. 6A to 6D SEM photographs of composite materials prepared by attaching more CNTs are shown in FIGS. 6A to 6D.
- the CNTs 5 are intertwined so that they are directly contacted or directly connected to each other without inclusions to form a network structure.
- the fiber bundle was immersed in the dissolved resin composition to obtain a tow prepreg.
- the traveling speed of the fiber bundle at this time was 1.5 m / min.
- the obtained tow prepreg was washed with MEK, one reinforcing fiber was taken out as a sample, and the interfacial adhesive strength was measured on the sample.
- a composite interface characteristic evaluation device manufactured by Toei Sangyo Co., Ltd., HM410
- microdroplets were prepared from a resin composition in an 80 ° C. atmosphere and heated under conditions of 125 ° C. ⁇ 1 hour.
- the microdroplet was formed using a thermosetting epoxy resin and a thermoplastic resin (manufactured by Ube Industries, Ltd., model number: nylon 6 (1013B)) as a resin composition.
- the sample 30 was sandwiched between blades 32 as shown in FIG. Next, the sample 30 is moved in the longitudinal direction (arrow direction in the figure) of the sample 30 at a speed of 0.12 mm / min, the sample 30 is pulled out from the microdroplet 34, and the maximum load when being pulled out by a load cell (not shown) F was measured. The measurement was performed five times for each sample at room temperature and in an air atmosphere.
- the interfacial shear strength ⁇ was calculated by the following formula (1), and the interfacial adhesive strengths of the examples and comparative examples were evaluated.
- F maximum load during drawing
- d fiber diameter
- L length in the drawing direction of the micro droplet.
- ⁇ F / (d ⁇ L) (1)
- the composite materials according to Examples 1 to 5 have an interfacial shear strength of about 10% compared to the fibers according to Comparative Examples 1 to 5, and the composite materials according to Examples 6 to 10 are comparative examples 6. It was confirmed that the fiber was improved by about 30% compared to the fibers according to -10. In the composite material according to the example, it is considered that the interfacial shear strength is improved by the thermosetting epoxy resin covering the fiber surface being reinforced by the CNT directly attached to the fiber surface.
- FIG. 8A and FIG. 8B are SEM photographs of the portions where the microdroplets of the samples according to Examples 6 to 10 and Comparative Examples 6 to 10 were peeled off after the composite material interface characteristics were evaluated.
- CNT and the resin composition are peeled off from the surfaces of the composite materials according to Examples 6 to 10, and a part of the fiber surface is exposed. From this, in Examples 6 to 10, it can be confirmed that the thermoplastic resin in the portion that is organically bonded to the CNTs in the 104 portion remains on the fiber surface, so that the heat provided on the fiber surface can be confirmed. It can be said that the interfacial shear strength has improved because the microdroplets formed of the plastic resin and the CNTs are organically bonded.
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Abstract
Description
(1)構成
図1に示すように複合素材1は、繊維3と、当該繊維3の表面に設けられたCNT5とを備える。
次に、複合素材1の製造方法を説明する。複合素材1は、CNT5を作製し、次いで当該CNT5を含む分散液を作製し、当該分散液を用いて繊維3表面にCNT5を付着させることにより製造することができる。以下、各工程について順に説明する。
CNT5としては、例えば特開2007-126311号公報に記載されているような熱CVD法を用いてシリコン基板上にアルミ、鉄からなる触媒膜を成膜し、CNT5の成長のための触媒金属を微粒子化し、加熱雰囲気中で炭化水素ガスを触媒金属に接触させることにより製造したものを用いる。アーク放電法、レーザ蒸発法などその他の製造方法により得たCNT5を使用することも可能であるが、CNT5以外の不純物を極力含まないものを使用することが好ましい。この不純物についてはCNT5を製造した後、不活性ガス中での高温アニールにより除去してもかまわない。この製造例で製造したCNT5は、直径が30nm以下で長さが数100μmから数mmという高いアスペクト比と直線性とを備えている。CNT5は単層、多層を問わないが、好ましくは、多層である。
次に、上記のように製造されたCNT5を用いて、CNT5がナノ分散した分散液を作製する。ナノ分散とは、CNT5が1本ずつ物理的に分離して絡み合っていない状態で溶液中に分散している状態を言い、2以上のCNT5が束状に集合した集合物の割合が10%以下である状態を意味する。
上記のようにして作製した分散液中に繊維3を浸漬した状態で、当該分散液に上記と同様に機械的エネルギーを付与しながら繊維3表面にCNT5を付着させる。
本実施形態の場合、CNT5は、繊維3表面に介在物無しの状態で付着しているので、繊維3表面からCNT5が剥離しにくい複合素材1を得ることができる。したがって複合素材1は、繊維本来の機能を発現可能とすると同時に、CNT由来の電気導電性、熱伝導性、機械強度等の機能を発揮することができる。
次に、第2実施形態に係る、強化繊維としてのトウプリプレグについて説明する。トウプリプレグは、複合素材1を複数、例えば数千~数万本程度束ねた複合素材束と、複合素材束の表面を覆う上記樹脂組成物とを備える。
(試料)
上記製造方法に示す手順で実施例に係る複合素材を作製した。CNTは熱CVD法によりシリコン基板上に直径10~15nm、長さ100μm以上に成長させたMW-CNT(Multi-Walled Carbon Nanotubes、多層カーボンナノチューブ)を用いた。CNTの触媒残渣除去には硫酸と硝酸の3:1混酸を用い、洗浄後に濾過乾燥した。
得られたトウプリプレグをMEKで洗浄して、1本の強化繊維を取り出して試料とし、試料に対し、界面接着強度を測定した。界面接着強度は、複合材界面特性評価装置(東栄産業(株)製、HM410)を用いた。まず80℃雰囲気中で試料に、樹脂組成物でマイクロドロップレットを作製し、125℃×1時間の条件で加熱した。マイクロドロップレットは、樹脂組成物として熱硬化性エポキシ樹脂、及び熱可塑性樹脂(宇部興産(株)製、型番:ナイロン6(1013B))を用いて形成した。
τ=F/(dπL)・・・(1)
3 繊維
5 カーボンナノチューブ(CNT)
18 複合素材束
24 トウプリプレグ(強化繊維)
102 繊維束
Claims (8)
- 繊維と、
前記繊維表面に設けられた複数のカーボンナノチューブと
からなる複合素材において、
前記複数のカーボンナノチューブが、前記繊維表面に直接付着していることを特徴とする複合素材。 - 前記複数のカーボンナノチューブは、介在物が無い状態で前記繊維表面に直接付着していることを特徴とする請求項1記載の複合素材。
- 前記介在物が、少なくとも分散剤であることを特徴とする請求項2記載の複合素材。
- 前記繊維が、直径が約3~150μmの繊維であることを特徴とする請求項1~3のいずれか1項記載の複合素材。
- 前記繊維が、炭素繊維であることを特徴とする請求項4記載の複合素材。
- 前記カーボンナノチューブは、長さ0.1~50μmで、かつ、直径30nm以下の多層であることを特徴とする請求項1~5のいずれか1項記載の複合素材。
- 前記カーボンナノチューブは、直径20nm以下であることを特徴とする請求項6記載の複合素材。
- 請求項1~7のいずれか1項に記載の複合素材と、前記複合素材表面を覆う樹脂組成物とを備えることを特徴とする強化繊維。
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CN201910327518.9A CN110055749B (zh) | 2014-10-23 | 2015-10-16 | 强化纤维的制造方法 |
US15/520,565 US20170314188A1 (en) | 2014-10-23 | 2015-10-16 | Composite Material and Reinforcing Fiber |
EP15852316.7A EP3211131A4 (en) | 2014-10-23 | 2015-10-16 | Composite material and reinforcing fiber |
KR1020177013411A KR102453189B1 (ko) | 2014-10-23 | 2015-10-16 | 복합 소재 및 강화 섬유 |
US16/259,987 US20190169792A1 (en) | 2014-10-23 | 2019-01-28 | Composite Material and Reinforcing Fiber |
US18/312,053 US20230304215A1 (en) | 2014-10-23 | 2023-05-04 | Method for producing composite material |
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US18/312,053 Continuation US20230304215A1 (en) | 2014-10-23 | 2023-05-04 | Method for producing composite material |
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KR20170074927A (ko) | 2017-06-30 |
US20230304215A1 (en) | 2023-09-28 |
EP3211131A4 (en) | 2018-06-13 |
KR102453189B1 (ko) | 2022-10-07 |
CN110055749B (zh) | 2022-03-22 |
EP3211131A1 (en) | 2017-08-30 |
JP6489519B2 (ja) | 2019-03-27 |
US20190169792A1 (en) | 2019-06-06 |
JP2016084547A (ja) | 2016-05-19 |
US20170314188A1 (en) | 2017-11-02 |
CN107075788A (zh) | 2017-08-18 |
CN110055749A (zh) | 2019-07-26 |
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