CN106390779B - Ptfe/pfsa共混膜 - Google Patents
Ptfe/pfsa共混膜 Download PDFInfo
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- CN106390779B CN106390779B CN201610555746.8A CN201610555746A CN106390779B CN 106390779 B CN106390779 B CN 106390779B CN 201610555746 A CN201610555746 A CN 201610555746A CN 106390779 B CN106390779 B CN 106390779B
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- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 31
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Abstract
本发明公开了一种包含与PFSA共混的PTFE的多孔膜及其制备方法,其中所述膜的CWST为至少约27达因/cm(约27×10‑5N/cm)。公开了过滤包含金属的流体的方法,所述方法包括使包含金属的流体经过所述多孔膜和从所述流体去除金属。公开了用于过滤SPM流体的方法,所述方法包括使所述SPM流体经过所述多孔膜和由所述流体去除颗粒。
Description
发明背景
PTFE膜,特别是膨胀PTFE(ePTFE)膜,被用于多种不同的液体和气体过滤应用中,包括涉及处理具有挑战性的流体例如腐蚀性或化学活性液体的应用。然而,对于多孔膜来说存在着这样的需求,其在可以过滤热的硫酸过氧化氢混合物(SPM)流体和/或表现出金属清除或者金属去除效率的同时提供低流动阻力。
本发明的这些和其它的优点将根据下文的描述而变得显而易见。
发明概述
本发明的一种实施方式提供了多孔膜,所述多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。
在另一种实施方式中,提供了一种用于过滤硫酸过氧化氢混合物(SPM)流体的方法,所述方法包括使所述流体经过多孔膜和由所述流体去除颗粒,所述多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。
在又一种实施方式中,提供了一种用于过滤包含金属的流体的方法,所述方法包括使包含金属的流体经过多孔膜和由所述流体去除金属,所述多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。
根据本发明的实施方式,还提供了包括所述膜的装置,和制备所述膜的方法。
发明详述
根据本发明的一种实施方式,多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。
在膜的一种实施方式中,PFSA为交联的,在另一种实施方式中,PFSA为未交联的。
在另一种实施方式中,提供了用于过滤SPM的方法,所述方法包括使所述流体经过多孔膜和从所述流体去除颗粒(例如包含二氧化硅的颗粒),所述多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。
根据本发明的一种实施方式中,用于过滤包含金属的流体的方法包括使包含金属的流体经过多孔膜和由所述流体去除金属,所述多孔膜包括与全氟磺酸(PFSA)共混的PTFE,其中所述膜的CWST为至少约27达因/cm(约27×10-5N/cm),在某些实施方式中,至少约30达因/cm(约30×10-5N/cm)。在所述方法的某些实施方式中,所述膜从流体去除第2族金属(例如Mg和/或Ca),多价金属和/或过渡金属(例如Cr、Mn、Fe和/或Ni)。
在另一种实施方式中,提供了制备膜的方法,所述方法包括使PTFE树脂和全氟磺酸(PFSA)混合,任选地还包括润滑剂;形成条带;拉伸所述条带以产生多孔膜;和在异丙醇中浸泡所述膜。
在另一种实施方式中,提供了制备多孔膜的方法,所述方法包括制备包括PTFE和PFSA的共混物,任选地与润滑剂混合;将共混物挤出为条带;双轴拉伸所述条带以获得多孔膜;任选地在约325℃的温度下使多孔膜退火约5分钟。
在根据本发明制备膜的某些实施方式中,包括交联剂,在其它实施方式中,不使用交联剂。
有利地,与其中使用金属试剂、并且所述金属试剂通过后洗涤处理(例如使用HCl)而去除以满足标准(例如在微电子工业中)的某些应用的膜的制备相比,根据本发明的膜可以不使用金属试剂来制备。另外地,与使用涂层来制备的膜相比,根据本发明的膜可被制备为制造后就具有功能性的,并且因为不存在涂层,不会不利地影响孔结构。此外,膜可以根据本发明以有利的制备方法来制备,例如,所述制备可以容易地结合至现有的制备方法中,获得提高的制备速度。
另外,与对照(未共混的)PTFE膜相比,根据本发明的膜的扫描电子显微图显示出类似的孔、原纤和节点结构。
根据本发明的多孔膜有利地提供了高金属清除或金属去除效率和低流动阻力的结合,同时使正在处理的流体保持为润湿的(即所述膜在处理流体中为未去湿的),并且适用于广泛范围的流体和气体(包括空气)过滤应用,包括无菌过滤应用。示例性的应用例如包括诊断应用(例如包括试样制备和/或诊断侧流设备)、喷墨应用、平版印刷例如作为对于HD/UHMW PE基媒介的替代、过滤制药工业的流体、金属去除、超纯水的制备、工业和地表水的处理、过滤用于医学应用的流体(包括家用和/或患者使用,例如静脉内应用,还例如包括过滤生物流体例如血液(例如病毒去除))、过滤用于电子工业的流体(例如过滤用于微电子工业中的光致抗蚀剂流体和热的硫酸过氧化氢混合物(SPM)流体)、用于食品和饮料工业的过滤流体、啤酒过滤、净化、过滤含抗体和/或含蛋白质的流体、过滤包含核酸的流体、细胞检测(包括原位检测)、细胞收获和/或过滤细胞培养流体。可替换地,或者另外地,根据本发明实施方式的多孔膜可被用于过滤空气和/或气体和/或可被用于通风应用(例如允许空气和/或气体、但不是液体通过)。根据本发明实施方式的多孔膜可被用于多种不同的设备中,包括外科设备和产品,例如眼外科产品。本发明的膜是尺寸稳定的。在某些实施方式中,多孔PTFE膜可单独地使用,例如作为非支撑膜,并且在其它实施方式中,多孔PTFE膜可与其它多孔元件和/或另一个部件组合使用,从而例如提供例如复合物、过滤元件和/或过滤器的制品。
在用于与PTFE共混时,合适的PFSA添加剂的一个例子可作为PFSA(例如AQUIVION PFSA D83-24B、AQUIVION PFSA D83-06A和AQUIVION PFSA D79-20BS)购自Solvay Specialty Polymers(Borger,Texas),其基于四氟乙烯和磺酰基氟代乙烯基醚(SFVE)F2C=CF-O-CF2-CF2-SO2F的短侧链(SSC)共聚物。离聚物分散液包含其磺酸形式。合适的PFSA添加剂的另一个例子为DuPontTM PFSA聚合物分散体。
在制备共混物时,PFSA的浓度可以根据不同的应用而变化。典型地,浓度为至少约0.05%;优选为约1%至约20%,更优选为约1%至约4%的范围。
根据本发明,多种不同的PTFE树脂(包括市售树脂)可以与PFSA共混。优选地,包括润滑剂。如本领域已知的,多种不同的润滑剂和润滑剂浓度是适用的。
膜可以根据现有技术已知那样来制备。根据需要,在结合PFSA和PTFE时,在与润滑剂物理混合之前,可以使用PTFE树脂来喷涂PFSA添加剂(例如用于改善分布)。
例如,所需量的PTFE粉末与PFSA溶液在合适的溶剂例如醇溶剂例如甲醇、乙醇或异丙醇中混合,从而获得共混物,其随后与润滑剂例如无味溶剂油例如Isopar G混合,并例如在双辊中使所获得的糊料经历剪切,并在约300psi或更大的压力下、至少两次、每次约55秒的时间来形成为型坯。使所获得的型坯在室温下平衡约12小时或更长。随后将型坯挤出为目标形状。例如,在26mm的模具间隙、最大压力和55℃的恒定温度下执行挤出,获得管形PTFE条带。接下来,沿着中心轴切开管形条带,围绕移液管再辊压,获得新的型坯(未压缩的)。新的型坯以与在第一次挤出操作中所使用的相同的条件再次挤出。加入该步骤从而为PTFE条带提供有利的交叉力学性能。压延在30℃下执行,目标条带厚度为9-10密耳,并切成4×4”。所获得的条带随后在125℃下干燥1h,由此从经挤出的条带去除润滑剂。
随后例如在如下的条件下拉伸所述条带:纵向(MD)和横向(TD)的拉伸比为3,拉伸速率300%/秒。拉伸炉中的温度设定为150℃。
经拉伸的条带随后进行退火。退火在退火炉中执行,随后冷却条带。通过如上的拉伸所产生的多孔性在冷却时仍保持。
不期望由任何特定的理论所限制,据信在异丙醇(IPA)中浸泡膜会暴露与所要处理的流体接触的更多表面,并改善金属清除能力。
膜可以具有任意合适的孔结构,例如孔尺寸(例如由起泡点或者例如在美国专利4,340,479中所描述的KL来证实,或者由毛细凝聚流动孔隙测量法来证实)、平均流动孔(MFP)尺寸(例如使用气孔计来表征,例如Porvai r Porometer(Porvair plc,Norfolk,UK),或者商标名为POROLUX的气孔计(Porometer.com;Belgium))、孔等级、孔径(例如使用例如在美国专利4,925,572中描述的改进的OSU F2测试来表征)、或者去除等级媒介。所使用的孔结构依赖于要使用的颗粒的尺寸,所要处理的流体的组成,和经处理的流体的希望的流出物含量。
典型地,根据本发明的多孔PTFE膜的孔等级为约1微米或更小,优选(特别是对于非去湿应用)为约0.05微米至约0.02微米,或更小。例如,所述膜可以是纳米多孔膜,例如,膜具有的孔径为1nm至100nm。
典型地,膜具有的厚度范围为约0.2至约5.0密耳(约5至约127微米),优选地,为约0.5至约1.0密耳(约13至约25微米),尽管膜可以比这些数值更厚或者更薄。
多孔膜可以具有任意的希望的临界润湿表面张力(CWST,例如在美国专利4,925,572中所限定的)。CWST可以通过依赖于一系列特定组成的溶液进行测定。每种溶液具有特定的表面张力。溶液的表面张力以小的不相等的增量由25达因/cm增加至92达因/cm。为了测量膜表面张力,所述膜被置于白光工作台的顶部,将一滴特定表面张力的溶液施加至膜表面,并记录液滴穿过膜并变为亮白色的时间,所述亮白色为光线经过所述膜的指示。当液滴穿透所述膜的时间≤10秒时,认为是立即润湿的。如果所述时间>10秒,那么认为溶液部分润湿所述膜。CWST可以根据本领域已知的进行选择,例如另外地例如在美国专利5,152,905、5,443,743、5,472,621和6,074,869中所公开的那些。
典型地,膜具有的CWST为至少约27达因/cm(约27×10-5N/cm),更优选地,至少约30达因/cm(约30×10-5N/cm),并且在某些实施方式中,至少约35达因/cm(约35×10-5N/cm)。例如,膜具有的CWST范围可以是约30达因/cm(约30×10-5N/cm)至约40达因/cm(约40×10- 5N/cm),或者更大。
膜具有第一多孔表面和第二多孔表面,以及第一多孔表面和第二多孔表面之间的本体,其中所述本体包括使用PFSA共混的PTFE。
包括多孔膜的制品,例如过滤器、过滤元件和/或复合物可以包括其它元件、层或部件,其可以具有不同结构和/或功能,例如如下的任意一个或多个中的至少一个:预过滤、支撑、排泄、间隔和缓冲。说明性地,过滤器还可以包括至少一个附加的元件,例如网和/或筛。
根据本发明的实施方式,膜、进滤元件、复合物和/或过滤器可以具有不同的构型,包括平面的、褶皱的、螺旋的和/或中空圆柱的。
膜、过滤元件、复合物和/或过滤器典型地被置于壳体中,所述专体包括至少一个入口和至少一个出口,并在所述入口和所述出口之间限定至少一个流体流动路径,其中所述膜横跨流体流动路径,从而提供过滤设备。优选地,对于交叉流动应用来说,膜、复合物和/或过滤器被置于壳体中,所述壳体包括至少一个入口和至少两个出口,并在入口和第一出口之间至少限定第一流体流动路径,以及在入口和第二出口之间限定第二流体流动路径,其中所述膜横跨第一流体流动路径以提供过滤设备。所述过滤设备可以是可灭菌的。可以使用具有合适形状并提供至少一个入口和至少一个出口的任何壳体。
所述壳体可以由任意合适的刚性不可渗透材料制得,包括任何不可渗透的热塑性材料,其为与所要处理的流体相容的。例如,所述壳体可以由金属例如不锈钢或者聚合物制得。在一种实施方式中,所述壳体为聚合物,例如丙烯酸系树脂、聚丙烯树脂、聚苯乙烯树脂或者聚碳酸化的树脂。
下文的实施例进一步描述了本发明,但是,当然不应当构成为对其范围进行任何方式的限定。
实施例1
本实施例说明了制备根据本发明实施方式使用不同浓度PFSA共混的膜的方法。
PTFE树脂与15phr润滑剂(EXXOL D80)和5phr、10phr以及20phr浓度的PFSA(24%w/w;AQUIVION PFSA 24;D83-24B Solvay Plastics)添加剂混合20分钟并平衡12小时。
通过在20巴下对混合物加压55秒两次,并在室温下平衡12小时来形成型坯。
以26mm间隙、最大压力和55℃的恒定温度进行挤出,获得管形PTFE条带。沿着中心轴切开管,并围绕移液管(pipette)再辊压,获得新的型坯。使用与在第一次挤出操作中所使用的相同条件再次挤出所述型坯。
在室温下执行压延,获得的条带的厚度为9-10密耳,长度和宽度尺寸为4×4英寸。在125℃下干燥条带1小时。拉伸所述条带,从而使得纵向(MD)和横向(TD)的拉伸比为1.5和3.0,拉伸速率300%/秒。拉伸炉中的温度设定为150℃,并且以350℃在退火炉中执行退火5秒。
在1∶1的异丙醇(IPA):去离子(DI)水中浸泡膜5天。
最高PFSA浓度(20phr)的膜以静态模式用硫酸过氧化氢混合物(SPM)进行测试,在140℃下持续3小时。
在DI水中洗涤膜(包括SPM测试过的膜)过夜并在160℃下干燥10分钟。
结果如下(与未使用PFSA共混的未经处理的(对照)PTFE膜进行比较):
本实施例示出根据本发明的实施方式,CWST为稳定增加的,提供未去湿的膜,即便是在暴露至SPM之后。
本文引用的所有参考文献,包括出版物、专利申请和专利,通过参考并入本文,引用程度如同各参考文献被单独和特别地说明以通过参考并入本文并且以其整体列举。
术语(冠词)“一个(a)”和“一种(an)”和“该(the)”以及类似的用语在描述本发明的上下文中(特别是在下面的权利要求的上下文中)被解释为覆盖单数和复数,除非本文另外说明或上下文明显矛盾。后接一系列的一个或多个项目的术语“至少一种”的(例如,“A和B中的至少一种”)的使用应理解为意味着选自所列项目中的一项(A或B)或两种或多种所列项目的任何组合(A和B),除非在此另外说明或通过上下文看出明显矛盾。术语“包含”,“具有”“包括”和“含有”解释为开放式的术语(意指“包括,但不限于”,),除非另外说明。本文中数值范围仅仅意指用作单独涉及的各个落入范围内的单个数值的简记方法,除非本文另外说明,各个单个的数值被合并到说明书中,如同其被本文单独引用。本文描述的所有方法可以按照任意合适的顺序实施,除非本文另外说明或上下文明显矛盾。任何一个和全部实例的使用,或本文提供的示例性语言(例如“如”、“例如”),仅仅意指更好地阐明发明,而不对发明的范围施加限制,除非另外声明。说明书中没有语言被解释为表明任何未声明的成分是实施本发明必不可少的。
本文描述了本发明的优选实施方式,包括发明人所知的实施发明的最佳模式。这些优选实施方式中的变体对于阅读了前述说明书的普通技术人员来说是显而易见的。发明人预计本领域技术人员适当时会采用这种变体,并且发明人还倾向于与本文详细描述不同地实施的发明。因此,本发明包括适用的法律所允许的本文所附的权利要求中记载的主题的所有改进和等同物。此外,本发明包括上述元素在所有可能的变体中的任意组合,除非本文另外说明或上下文明显矛盾。
Claims (4)
1.制备多孔膜的方法,所述多孔膜具有1nm至100nm的孔径,所述方法包括:
将PTFE树脂和全氟磺酸(PFSA)聚合物溶液和醇溶剂组合,任选地还包括润滑剂;
形成条带;
拉伸所述条带以产生多孔膜;和
在异丙醇(IPA)中浸泡所述多孔膜,其中不使用金属试剂来制备所述多孔膜。
2.权利要求1的方法,进一步包括干燥所述膜。
3.权利要求1或2的方法,其中当将PTFE树脂与PFSA聚合物溶液组合时,PFSA聚合物溶液的PFSA聚合物浓度为1重量%至4重量%。
4.由权利要求1的方法制备的多孔PTFE膜。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6179132B1 (en) * | 1998-03-13 | 2001-01-30 | Millipore Corporation | Surface modified polymeric substrate and process |
CN1319908A (zh) * | 2000-03-31 | 2001-10-31 | 旭硝子株式会社 | 用于聚合物电解质燃料电池的电解质膜及其制造方法 |
CN101085418A (zh) * | 2006-11-30 | 2007-12-12 | 中国人民解放军总后勤部军需装备研究所 | 一种聚四氟乙烯纳米孔径滤膜的加工方法 |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU529368B2 (en) | 1978-05-15 | 1983-06-02 | Pall Corporation | Preparing polyamide membrane filter media and product |
US4925572A (en) | 1987-10-20 | 1990-05-15 | Pall Corporation | Device and method for depletion of the leukocyte content of blood and blood components |
US4902308A (en) * | 1988-06-15 | 1990-02-20 | Mallouk Robert S | Composite membrane |
US5152905A (en) | 1989-09-12 | 1992-10-06 | Pall Corporation | Method for processing blood for human transfusion |
US5082472A (en) * | 1990-11-05 | 1992-01-21 | Mallouk Robert S | Composite membrane for facilitated transport processes |
US5443743A (en) | 1991-09-11 | 1995-08-22 | Pall Corporation | Gas plasma treated porous medium and method of separation using same |
CA2083075A1 (en) | 1992-06-10 | 1993-12-11 | Vlado I. Matkovich | System for treating transition zone material |
WO1996003194A1 (en) | 1994-07-28 | 1996-02-08 | Pall Corporation | Fibrous web and process of preparing same |
JP2626577B2 (ja) * | 1994-09-28 | 1997-07-02 | 日本電気株式会社 | フィルタ |
US5599614A (en) * | 1995-03-15 | 1997-02-04 | W. L. Gore & Associates, Inc. | Integral composite membrane |
JPH11204486A (ja) * | 1998-01-09 | 1999-07-30 | Mitsubishi Electric Corp | 硫酸−過酸化水素洗浄槽の連続的運転方法 |
US6495209B1 (en) * | 1998-02-20 | 2002-12-17 | Lynntech, Inc. | Process of making a composite membrane |
WO2000063995A1 (en) * | 1999-04-20 | 2000-10-26 | Lynntech, Inc. | Process of making a composite membrane |
EP2324906B1 (en) * | 2000-05-24 | 2014-09-10 | EMD Millipore Corporation | Multilayered membranes |
WO2002081056A1 (fr) * | 2001-04-05 | 2002-10-17 | Daikin Industries, Ltd. | Materiau filtrant pour filtre, cartouche de filtre, module de filtre utilisant cette cartouche, et procede d'elaboration de ce materiau filtrant |
JP2003045449A (ja) * | 2001-08-01 | 2003-02-14 | Masaru Ichikawa | 化学発電/有機ハイドライド製造装置および化学発電/有機ハイドライド製造方法 |
JP4709995B2 (ja) * | 2004-05-17 | 2011-06-29 | 国立大学法人富山大学 | 廃液に含有される有用金属の回収方法 |
JP2007042912A (ja) * | 2005-08-04 | 2007-02-15 | Toshiba Corp | 基板洗浄装置および基板洗浄方法 |
WO2007058698A2 (en) * | 2005-09-13 | 2007-05-24 | Rasirc | Method of producing high purity steam |
JP4808551B2 (ja) * | 2006-06-16 | 2011-11-02 | クロリンエンジニアズ株式会社 | 過硫酸の製造方法 |
JP5087325B2 (ja) * | 2006-06-16 | 2012-12-05 | 株式会社東芝 | 洗浄システム及び洗浄方法 |
JP2009170692A (ja) * | 2008-01-17 | 2009-07-30 | Renesas Technology Corp | 半導体装置の製造方法および半導体ウエハ洗浄装置 |
JP5156504B2 (ja) * | 2008-06-25 | 2013-03-06 | 日本ゴア株式会社 | 複合膜及びそれを用いた水分量調整モジュール |
JP5703563B2 (ja) * | 2008-09-12 | 2015-04-22 | 東レ株式会社 | 複合半透膜およびその製造方法 |
US20100167100A1 (en) * | 2008-12-26 | 2010-07-01 | David Roger Moore | Composite membrane and method for making |
JP6026087B2 (ja) * | 2011-07-29 | 2016-11-16 | 株式会社Screenホールディングス | 基板処理装置、フィルタ洗浄方法、およびフィルタ洗浄装置 |
US20130112621A1 (en) * | 2011-11-03 | 2013-05-09 | Lei Zheng | Water filtration article and related methods |
JP5830654B2 (ja) * | 2012-06-28 | 2015-12-09 | パナソニックIpマネジメント株式会社 | 高分子電解質膜の製造方法 |
US20170028359A1 (en) * | 2015-07-31 | 2017-02-02 | Pall Corporation | Coated ptfe membrane |
-
2015
- 2015-07-31 US US14/815,031 patent/US20170028361A1/en not_active Abandoned
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2016
- 2016-05-13 EP EP16169674.5A patent/EP3130390B1/en active Active
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- 2016-05-16 JP JP2016098054A patent/JP6260016B2/ja active Active
- 2016-05-31 CN CN201610555746.8A patent/CN106390779B/zh active Active
- 2016-05-31 TW TW105117023A patent/TWI621653B/zh active
- 2016-05-31 KR KR1020160066929A patent/KR101915280B1/ko active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6179132B1 (en) * | 1998-03-13 | 2001-01-30 | Millipore Corporation | Surface modified polymeric substrate and process |
CN1319908A (zh) * | 2000-03-31 | 2001-10-31 | 旭硝子株式会社 | 用于聚合物电解质燃料电池的电解质膜及其制造方法 |
CN101085418A (zh) * | 2006-11-30 | 2007-12-12 | 中国人民解放军总后勤部军需装备研究所 | 一种聚四氟乙烯纳米孔径滤膜的加工方法 |
Also Published As
Publication number | Publication date |
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EP3130390A1 (en) | 2017-02-15 |
KR101915280B1 (ko) | 2018-11-05 |
KR20170015120A (ko) | 2017-02-08 |
US20170028361A1 (en) | 2017-02-02 |
CN106390779A (zh) | 2017-02-15 |
TWI621653B (zh) | 2018-04-21 |
JP2017039117A (ja) | 2017-02-23 |
EP3130390B1 (en) | 2021-03-24 |
SG10201603823SA (en) | 2017-02-27 |
TW201704326A (zh) | 2017-02-01 |
JP6260016B2 (ja) | 2018-01-17 |
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