WO2014104730A1 - 연속 탄소섬유 강화 열가소성 프리프레그의 제조 방법 - Google Patents
연속 탄소섬유 강화 열가소성 프리프레그의 제조 방법 Download PDFInfo
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- WO2014104730A1 WO2014104730A1 PCT/KR2013/012144 KR2013012144W WO2014104730A1 WO 2014104730 A1 WO2014104730 A1 WO 2014104730A1 KR 2013012144 W KR2013012144 W KR 2013012144W WO 2014104730 A1 WO2014104730 A1 WO 2014104730A1
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- prepreg
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- continuous carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B38/18—Handling of layers or the laminate
- B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
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- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
- B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
- B29C65/1403—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the type of electromagnetic or particle radiation
- B29C65/1425—Microwave radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
- B29C70/506—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
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- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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Definitions
- the present invention relates to a method for producing a continuous carbon fiber reinforced thermoplastic prepreg, and more particularly, after developing and arranging carbon fibers between a plurality of layers of thermoplastic resin films without directly impregnating carbon fibers into a molten thermoplastic resin. It relates to a method for producing a continuous carbon fiber reinforced thermoplastic prepreg through the bonding process.
- Continuous Carbon Fiber Reinforced Thermoplastic has a continuous phase of reinforcing fibers such as glass fiber or carbon fiber in a plastic having relatively weak mechanical strength.
- Reinforced plastics are 5 to 50 mm long, such as short fiber-reinforced thermoplastics (LFT) or long fiber-reinforced thermoplastics (LFT) or glass mat-reinforced thermoplastics (GMT) Compared with long-fiber reinforced plastics, its mechanical strength, rigidity and impact performance are very good.
- the continuous fiber-reinforced plastic is excellent in flexibility and can be woven in one direction or in both directions, through which the continuous fiber-reinforced plastic structure can be applied to products requiring a variety of mechanical performance.
- Such continuous fiber reinforced plastics are typically produced by a pultrusion method or a mixed to hot pressing method.
- the pultrusion method is a method of impregnating a plastic resin in a continuous fiber bundle by passing a wide spread continuous fiber bundle through a liquid or molten resin bath or a die.
- a plastic resin in a continuous fiber bundle by passing a wide spread continuous fiber bundle through a liquid or molten resin bath or a die.
- the film is melted from the surface, there is a problem that the surface is easily bent.
- one aspect of the present invention is a high-concentration rate (Micro-impregnation) by the micro-impregnation process including the repeated lamination, melting and impregnation process of the film and the widened carbon fiber bundle without going through a high viscosity thermoplastic polymer pellet melt resin impregnation process ( 12K, 24K, 48K, etc.) to improve the impregnation of the resin to the carbon fiber bundles, to maximize the volume fraction containing continuous carbon fiber, to reduce the generation of void (void), easy to manufacture, high strength continuous carbon fiber reinforcement It is to provide a method for producing a thermoplastic prepreg.
- thermoplastic film on at least some of upper and lower portions of the widened carbon fibers; And it is provided in the method for producing a continuous carbon fiber reinforced thermoplastic prepreg comprising the step of bonding the thermoplastic film and carbon fibers constituting the laminate to produce a bonded body.
- the step of preparing the conjugate is preferably carried out by irradiating the microwave.
- the step of preparing the conjugate is preferably performed by at least one heat source selected from the group consisting of halogen lamps and infrared lamps with a temperature of 150 to 400 °C.
- the plurality of widened carbon fibers are arranged at regular intervals.
- the carbon fibers are coated with a bonding resin having a lower melting temperature than the thermoplastic film.
- thermoplastic film is preferably selected from the group consisting of polypropylene (PP), polyamide (PA), polyether ether ketone (PEEK) and polyethylene terephthalate (PET).
- PP polypropylene
- PA polyamide
- PEEK polyether ether ketone
- PET polyethylene terephthalate
- the thickness of the said thermoplastic film is 10-100 micrometers.
- the manufacturing method of the present invention preferably further comprises the step of pressing by vacuum or atmospheric pressure by a pair of rollers.
- the pressing step is preferably performed at a temperature of 100 to 450 °C.
- the manufacturing method of the present invention comprises the steps of heating; And vacuum or atmospheric pressure compression by an additional pair of rollers.
- the heating step is preferably carried out at a temperature of 100 to 450 °C depending on the thermoplastic resin or film applied.
- the heating step is preferably performed by at least one heat source selected from the group consisting of halogen lamps and infrared lamps.
- the laminate is preferably produced including a thermoplastic film laminated in two or more layers and carbon fibers disposed between the thermoplastic films.
- the pre- or pre-impregnated continuous carbon fiber-reinforced prepreg (continuous carbon fiber-containing tape) of the thermoplastic resin film is subjected to a uni-directional arrangement or bi-axial (0 degree, 90 degrees). After the arrangement, a separate resin impregnation process is not required, and the thermoplastic prepreg obtained by the present invention is unidirectionally arranged or woven and then hot pressed to form a continuous carbon fiber-reinforced thermoplastic type carbon fiber reinforcement plate of various forms of high strength and light weight. Can be obtained.
- thermoplastic films While being easy to weave, various kinds of thermoplastic films may be applied, and a continuous carbon fiber reinforced thermoplastic prepreg (continuous carbon fiber-containing tape) having excellent uniformity may be obtained.
- thermoplastic resin having a relatively high viscosity compared to the thermosetting resin during manufacture, it minimizes the voids (poid) in the molded body and maximizes the volume fraction of the carbon fiber, high-strength thermoplastic carbon fiber composite material ( Carbon Fiber Reinforced Thermo-Plastics (CFRTP) parts can be manufactured.
- CFRTP Carbon Fiber Reinforced Thermo-Plastics
- FIG 1 shows briefly the flow of the manufacturing process of the present invention.
- FIG. 2 exemplarily shows a carbon fiber tow wide opening machine (Japanese Harmoni-industry Co., Ltd.) that can be used to provide a plurality of widened carbon fibers of the present invention.
- Figure 4 schematically shows a perspective view of a carbon fiber reinforced thermoplastic film produced by the present invention.
- Figure 5 (a) and (b) is a cross-sectional view of the carbon fiber reinforced thermoplastic prepreg produced by the present invention, respectively, at different magnifications.
- Figure 6 shows an exemplary process for producing a unidirectional CFRTP plate using the thermoplastic prepreg (continuous carbon fiber containing tape) of the present invention.
- Figure 7 shows an exemplary process for producing a woven CFRTP plate using the thermoplastic prepreg (continuous carbon fiber containing tape) of the present invention.
- Figure 8 (a) shows the bending performance test apparatus
- Figure 8 (b) shows a specimen for the bending performance test.
- Figure 9 shows the results of evaluating the bending performance of the unidirectional CFRTP plate produced by using the thermoplastic prepreg of the present invention.
- FIG. 10 is a SEM analysis of the cross-sectional view of the exemplary plate of the present invention at different magnifications.
- a continuous carbon fiber reinforced thermoplastic prepreg including a process of arranging and bonding carbon fibers on one surface of a thermoplastic film or between a plurality of thermoplastic films without directly impregnating the carbon fibers with the molten thermoplastic resin.
- the method of the present invention comprises the steps of providing a plurality of carbon fiber widened; Preparing a laminate by disposing a thermoplastic film on at least some of upper and lower portions of the widened carbon fibers; And bonding the thermoplastic film constituting the laminate and the continuous carbon fibers to produce a bonded body.
- a prepreg in which a continuous carbon fiber is bonded or fused to a thermoplastic film is obtained, which may also be referred to herein as a "bond” or a “semi prepreg". Furthermore, the "semi prepreg” may be finally obtained through a press or heating process such that the final prepreg of the carbon fiber is inserted into the thermoplastic film.
- the prepreg of the present invention is meant to include all the forms such as tape (tape) and sheet (sheet).
- Figure 1 schematically shows a flow chart of the manufacturing method of the present invention to look at the present invention with reference to this, the step of providing the plurality of carbon fibers in the present invention specifically the step of unwinding the carbon fiber and the bundle of carbon fiber Spreading may include.
- a plurality of continuous carbon fiber tows are provided while being unwound in a carbon fiber unwinding roller, and a plurality of spreading rollers are used to uniformly unfold the carbon fiber tow thus unwound. This can be widened at a desired interval in the width direction.
- the deploying of the carbon fibers is carried out so that the tow-shaped bundles of carbon fibers pass through respective holes formed in the fiber separating apparatus, so that the respective carbon fibers are not entangled with each other in one direction. Can be arranged.
- FIG. 2 exemplarily shows a carbon fiber carding machine (Japanese Harmoni-industry Co., Ltd.) that can be used in the step of providing a plurality of widened carbon fibers of the present invention.
- Fig. 2 (c) is a photograph when opening the continuous carbon fiber tow.
- the carbon fiber bundle 12K fiber diameter 5-7 ⁇ m, 12,000 strand focused yarn
- the carbon fiber bundle 24K fiber diameter 5-7 ⁇ m, 24,000 strand focused yarn
- the case of 5mm to 70mm and in the case of 48K carbon fiber bundle (fiber diameter 5 ⁇ 7 ⁇ m, 48,000 strand focused yarn) it is preferable to open from 5mm to 100mm.
- the widened plurality of carbon fibers may be arranged at regular intervals, but is not limited thereto and may be arranged to be adjusted at irregular intervals as necessary. Furthermore, the plurality of widened carbon fiber bundles can be uni-directional (Uni-Directional) arrangement, as well as can be produced in a variety of weave patterns (Plain, Twill, Satin, etc.) if necessary.
- thermoplastic film constituting the laminate and carbon fibers are bonded to produce a semiprepreg bonded body.
- steps. 3 exemplarily shows that the widened carbon fiber bundle and the thermoplastic film form the laminate of the present invention.
- the laminate may basically include one thermoplastic film and one carbon fiber layer, and further include a thermoplastic film on the upper and lower portions of the carbon fiber layer, or may include a carbon fiber layer on the upper and lower portions of the thermoplastic film. If necessary, the above-described combination of layers may be sequentially stacked.
- the thickness of each of the thermoplastic films is preferably 10 to 100 ⁇ m, more preferably 15 to 30 ⁇ m, and when the thickness is less than 10 ⁇ m, there is no problem in performing the manufacturing process, There is a problem, and if it exceeds 100 ⁇ m there is a problem that uniform impregnation may be lowered.
- the step of preparing the conjugate may be performed by irradiating microwaves in consideration of melting points of various thermoplastic bonding layers and resin films, or may be performed by at least one heat source selected from the group consisting of halogen lamps and infrared lamps.
- Irradiation of the microwave may be carried out by a microwave device, by the microwave irradiation the carbon fiber absorbs the heat of the microwave prior to the thermoplastic film to generate heat, the heat generated so that the thermoplastic film
- the melted thermoplastic film may be first fused at the contact point of the carbon fiber and stably laminated.
- thermoplastic film constituting the laminate and the carbon fiber is stably fused.
- the carbon fiber is preferably coated with a bonding resin having a lower melting temperature than the thermoplastic film. That is, the carbon fiber is different depending on the type of the mattress (Matrix) resin to be impregnated, but preferably coated with a bonding resin selected from the group consisting of a thermoplastic resin having a lower melting temperature than the mattress (Matrix) resin.
- thermoplastic film and the carbon fiber coated by the coating layer are bonded even though the separate heat source is not used.
- the bonding resin selected here is melted at the same series or at a low temperature, the bonding resin is melted before the impregnating film resin is melted, and the common thermoplastic resin which can be melted and bonded to the impregnating film layer is collectively referred to.
- thermoplastic film is preferably selected from the group consisting of polypropylene (PP), polyamide (PA), polyether ether ketone (PEEK), and polyethylene terephthalate (PET), but is not limited thereto.
- the bonding resin is preferably selected from a variety of low-temperature thermoplastic resin, such as Co-polyamide series, Co-polyester series.
- the form in which the interface between the carbon fiber and the thermoplastic film is fused or bonded as described above is referred to as "semi-prepreg" or "bonded body", and as such a bonded body is formed, this is a pressurized hot roller. This allows the lamination arrangement of the film and the carbon fiber bundles to be maintained in subsequent processes such as passing through.
- the step of pressing by vacuum or atmospheric pressure pressing by a pair of rollers may be further performed, and by such a step, the thermoplastic film is melted to form a prepreg in which a resin is inserted into the carbon fiber. It can manufacture.
- the pressing step is preferably carried out at a temperature of 100 to 450 °C according to the type of thermoplastic resin, so that the thermoplastic film is melted to easily insert the carbon fiber, the smaller is preferably in the range of 150 to 300 °C. If the pressing step is carried out below 100 °C there is a problem that the thermoplastic film is insufficiently melted to insert the carbon fiber, if the pressing step is carried out above 450 °C, any thermoplastic resin or film is degraded or In particular, burning may occur, and it is necessary to apply the optimum temperature depending on the thermoplastic resin to be applied.
- the step of heating and vacuum or atmospheric pressure pressing by an additional pair of rollers may be further performed, in which case the insertion This can be done more completely.
- the heating step is preferably carried out at a temperature of 100 to 450 °C according to the type of the thermoplastic resin and the film, the further pressing step is preferably carried out at a temperature of 100 to 450 °C.
- the heating step is preferably set to a higher temperature than the pressing step performed before and after within the above range.
- the heating step and the additional compression step overlap the temperature range, but the actual setting temperature causes the heating step within this range to be higher than the additional compression step. That is, when such an additional step is carried out, bubbles remaining in the laminate of the thermoplastic film and the widened carbon fiber can be more easily and completely removed by the compression method. On the other hand, in the case of a vacuum atmosphere, such bubbles are more easily removed, and the remaining of bubbles can be further minimized.
- the heating may be performed by at least one heat source selected from the group consisting of a halogen lamp and an infrared lamp, but is not limited thereto.
- the method of the present invention may further include a step of natural cooling at room temperature in order to lower the temperature.
- This cooling step may be performed by injection of air, but is not limited thereto.
- the step of winding the film or tape manufactured on a winding roll may be performed while performing such cooling.
- the laminate constituting the continuous carbon fiber reinforced thermoplastic prepreg produced by the method of the present invention is produced by including a plurality of layers of thermoplastic film and a carbon fiber layer disposed between each thermoplastic film, or a plurality of layers of carbon It may include a fiber layer, and a thermoplastic film disposed between each carbon fiber layer.
- the laminate is preferably produced including a thermoplastic film laminated in two or more layers and carbon fibers disposed between the thermoplastic films.
- FIG. 4 schematically shows a continuous carbon fiber reinforced thermoplastic prepreg formed by pressing two carbon fiber layers between three thermoplastic films.
- the method for producing a continuous carbon fiber reinforced thermoplastic prepreg of the present invention further includes winding the continuous carbon fiber reinforced thermoplastic prepreg prepared by the present invention on a winding roller while being supported by a tension roller as shown in FIG. 1. can do.
- FIG. 5 (a) and (b) is a cross-sectional view of the carbon fiber reinforced thermoplastic prepreg produced by the present invention, respectively, at different magnifications.
- thermoplastic CFRP with continuous fibers until now.
- a semiprepreg and a prepreg can be obtained by inserting a thermoplastic resin film having a thickness of 10 to 100 ⁇ m between the widened tens of ⁇ m thick carbon fiber bundle layers and then bonding the thermoplastic resin film.
- the intermediate material is needed to produce a CFRP molded product which is completely impregnated with the resin by maximizing the impregnation rate of the resin in the bundle of carbon fibers while minimizing the high viscosity melt flow.
- Semiprepregs and prepregs, including tape and sheet forms, can be obtained.
- the carbon fiber is a conventional reinforcing fiber, such as glass fibers, aramid fibers, ceramic fibers, organic fibers such as metal fibers, inorganic fibers, metal fibers, etc. It is a widely applicable alternative.
- the prepreg obtained by the present invention can produce a unidirectional CFRTP plate through the exemplary process shown in FIG. 6, and more specifically, a semiprepreg or prepreg bonded with a thermoplastic film by opening a carbon fiber tow. After manufacturing the legs and array molding it can be produced a one-way CFRTP plate.
- the array pattern can be biaxially (0 degrees, 90 degrees), or multi-axis (0 degrees, 45 degrees, 90 degrees, -45 degrees, O degrees) and variously arranged CFRTP ( Carbon Fiber Reinforced Thermo-Plastic) can be manufactured.
- CFRTP Carbon Fiber Reinforced Thermo-Plastic
- the prepreg obtained by the present invention can also produce a woven CFRTP plate through the exemplary process shown in Figure 7, more specifically, a semi-prepreg bonded to a thermoplastic film by opening a carbon fiber tow After the manufacture of the weaving it can be produced a woven CFRTP plate material. If desired, weaving can be performed in a variety of weave patterns (Plain, Twill, Satin, etc.).
- the CFRTP plate obtained using the prepreg of the present invention has excellent bending performance.
- the CFRTP sheet according to the present invention is composed of PA6 composite products (trade name Celstran CFT-TP PA6 CF60-01) containing 48 Vol% of carbon fiber (CF) of an advanced company (Ticona). In contrast, it was confirmed that the flexural strength exceeded 100 MPa or more.
- CFRTP carbon fiber 48Vol% composite product
- FIG. 10 is a SEM analysis of the cross-sectional view of the exemplary plate of the present invention at different magnifications.
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Abstract
Description
Claims (14)
- 광폭화된 복수 개의 탄소섬유를 제공하는 단계;상기 광폭화된 탄소섬유의 상부 및 하부 중 적어도 일부에 열가소성 필름을 배치하여 적층체를 제조하는 단계; 및상기 적층체를 구성하는 열가소성 필름과 탄소섬유를 접합하여 접합체를 제조하는 단계를 포함하는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 접합체를 제조하는 단계는 마이크로웨이브를 조사하여 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 접합체를 제조하는 단계는 100 내지 450℃의 할로겐 램프 및 적외선 램프로 이루어지는 그룹으로부터 선택되는 적어도 하나의 열원에 의해 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 광폭화된 복수 개의 탄소섬유는 일정한 간격으로 배치되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 광폭화된 복수 개의 탄소섬유를 제공하는 단계에 있어서 상기 탄소섬유는 상기 열가소성 필름보다 용융 온도가 낮은 접합용 수지로 코팅된 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 열가소성 필름은 폴리프로필렌(PP), 폴리아미드(PA), 폴리에테르에테르케톤(PEEK) 및 폴리에틸렌테레프탈레이트(PET)로 이루어진 그룹으로부터 선택되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 열가소성 필름의 두께는 10 내지 100㎛인 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 한 쌍의 롤러에 의한 진공 또는 상압 압착에 의해 압착하는 단계를 추가로 포함하는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제8항에 있어서, 상기 압착하는 단계는 100 내지 450℃의 온도에서 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제8항에 있어서,가열하는 단계; 및추가의 한 쌍의 롤러에 의해 진공 또는 상압 압착하는 단계를 더욱 포함하는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제10항에 있어서, 상기 가열하는 단계는 100 내지 450℃의 온도에서 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제10항에 있어서, 추가의 압착하는 단계는 100 내지 450℃의 온도에서 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제10항에 있어서, 상기 가열하는 단계는 할로겐 램프 및 적외선 램프로 이루어지는 그룹으로부터 선택되는 적어도 하나의 열원에 의해 수행되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
- 제1항에 있어서, 상기 적층체는 적층된 열가소성 필름 및 열가소성 필름 사이에 배치된 탄소섬유를 포함하여 제조되는 연속 탄소섬유 강화 열가소성 프리프레그의 제조방법.
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EP13868399.0A EP2939832B1 (en) | 2012-12-27 | 2013-12-24 | Method for preparing continuous carbon fiber-reinforced thermoplastic prepreg |
CN201380068419.4A CN104903104B (zh) | 2012-12-27 | 2013-12-24 | 连续碳纤维增强热塑性预浸料的制造方法 |
JP2015549278A JP6149123B2 (ja) | 2012-12-27 | 2013-12-24 | 連続炭素繊維強化熱可塑性プリプレグの製造方法 |
US14/654,835 US9873242B2 (en) | 2012-12-27 | 2013-12-24 | Method for preparing continuous carbon fiber-reinforced thermoplastic prepreg |
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KR1020120154591A KR101449204B1 (ko) | 2012-12-27 | 2012-12-27 | 연속 탄소섬유 강화 열가소성 프리프레그의 제조 방법 |
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EP2939832A4 (en) | 2016-02-17 |
US9873242B2 (en) | 2018-01-23 |
KR20140085713A (ko) | 2014-07-08 |
US20150336369A1 (en) | 2015-11-26 |
CN104903104B (zh) | 2018-02-02 |
JP6149123B2 (ja) | 2017-06-14 |
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