CN103298993A - 拨水性织物及衣料 - Google Patents

拨水性织物及衣料 Download PDF

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CN103298993A
CN103298993A CN2011800586101A CN201180058610A CN103298993A CN 103298993 A CN103298993 A CN 103298993A CN 2011800586101 A CN2011800586101 A CN 2011800586101A CN 201180058610 A CN201180058610 A CN 201180058610A CN 103298993 A CN103298993 A CN 103298993A
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fabric
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CN103298993B (zh
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岩下宪二
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Teijin Frontier Co Ltd
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Teijin Fibers Ltd
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    • D02G3/28Doubled, plied, or cabled threads
    • D02G3/286Doubled, plied, or cabled threads with alternatively "S" and "Z" direction of twist, e.g. Self-twist process
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    • D02J1/00Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/08Interlacing constituent filaments without breakage thereof, e.g. by use of turbulent air streams
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    • D03D15/30Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the fibres or filaments
    • D03D15/33Ultrafine fibres, e.g. microfibres or nanofibres
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Abstract

本发明提供一种环保的、具有优异拨水性的拨水性织物及使用该拨水性织物制成的衣料。所述拨水性织物用以下方法得到:将包含具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱的复合纱使用在经纱或纬纱中而得到织物后,使全氟辛酸及全氟辛烷磺酸的合计浓度为0~5ng/g的氟系拨水剂附着在该织物上。

Description

拨水性织物及衣料
技术领域
本发明涉及一种环保的、具有优异拨水性的拨水性织物及使用该拨水性织物制成的衣料。
背景技术
一直以来,在运动衣料、休闲衣料、伞布等领域需要有拨水性布料,并使氟系拨水剂等拨水剂附着在布料上(例如可参见专利文献1、专利文献2)。
此外,近年来,为了保护环境,有人提出使可能对生物造成影响的化合物(例如全氟辛酸、全氟辛烷磺酸等)的含量小的氟系拨水剂附着到布料上(例如可参见专利文献3)。
专利文献1:日本特开昭60-94645号公报
专利文献2:日本特开昭61-70043号公报
专利文献3:日本特开昭2007-247089号公报
发明内容
本发明者发现,附着有全氟辛酸(以下有时也称“PFOA”)、全氟辛烷磺酸(以下有时也称“PFOS”)等的含量小的氟系拨水剂的布料虽是环保布料,但在拨水性这一点上并不充分。本发明是鉴于该背景而完成的,其目的在于提供一种环保的、具有优异拨水性的拨水性织物及使用该拨水性织物制成的衣料。
为了完成上述课题,本发明者进行了深入研究,结果发现,在将PFOA、PFOS等的含量小的氟系拨水剂施用到布料上时,作为布料,若使用在经纱和纬纱中的至少一方织入了包含有具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱的复合纱的织物,则织物表面会形成莲叶状微细凹凸,由此,可获得优异的拨水性。并进一步进行了深入的研究,从而完成了本发明。
因此,根据本发明,提供“织物上附着有全氟辛酸和全氟辛烷磺酸的合计浓度为0~5ng/g的氟系拨水剂的拨水性织物,其特征在于,使用包含有具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱的复合纱(composite yarn)”。
此时,构成上述复合纱的纤维的单丝纤度(single yarn fineness)优选在1dtex以下。此外,在上述复合纱中,单丝根数(number of filaments)优选在50根以上。此外,上述复合纱的卷缩率(crimp degree)优选在13%以上。另外,上述复合纱优选经过交织加工,交织个数为35~90个/m。还有,织物的覆盖系数优选在1500~2800的范围内。再有,织物优选经过轧光加工。另外,织物表面优选形成有莲叶状微细凹凸。还有,按JIS L1018测得的织物的膨松性优选在1.30以上。再有,织物的拨水滚动角度优选在22度以下。
另外,根据本发明,提供使用上述拨水性织物制成的衣料。
根据本发明,提供一种环保的、具有优异拨水性的拨水性织物及使用该拨水性织物制成的衣料。
具体实施方式
下面对本发明的实施方式进行详细说明。
首先,本发明的拨水性织物上附着有全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)的合计浓度(即拨水剂1g中所含的PFOA浓度和PFOS浓度合计)为0~5ng/g(纳克/克)的氟系拨水剂。
这里,在用高效液相色谱–质谱仪(LC–MS)进行测定时,每1g拨水剂中PFOA和PFOS的合计浓度在5ng/g以下(优选小于1ng/g,更优选PFOA和PFOS中的至少任一方的浓度为0ng/g,尤其优选PFOA浓度和PFOS浓度均为0ng/g)。PFOA和PFOS的合计浓度大于5ng/g时,从环境角度上讲,不适宜。
作为PFOA和PFOS的合计浓度为0~5ng/g(纳克/克)的氟系拨水剂,可列举出仅由不含N-羟甲基的单体构成的全氟烷基丙烯酸酯共聚物、市售物等。市售物中,适宜例子有旭硝子公司生产的氟系拨水剂AsahiGuard E系列AG-E061、住友3M公司生产的ScotchGuard PM3622、PM490、PM930等。
本发明的拨水性织物中织入有包含有具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱的复合纱。通过在织物中织入该复合纱,织物表面会形成有莲叶状微细凹凸,从而得到优异的拨水性。
这里,作为假捻卷缩加工的条件,可以列举出以下方法:使纱条经过第1辊、设定温度为90~220℃(更优选100~190℃)的热处理加热箱,通过加捻装置进行加捻的方法;在上述加捻后,再根据需要将纱条导入第2加热箱区域进行松弛热处理的方法。假捻加工时的延伸倍率优选在0.8~1.5的范围内。此外,在假捻数(T/m)=(32500/√Dtex)×α的式子中,优选α=0.5~1.5。尤其优选α=0.8~1.2。作为使用的加捻装置,圆盘式或带式的摩擦式加捻装置容易卷线,断纱也少,因而优选。也可以是销式加捻装置。
此外,若上述复合纱是在将具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱并拢后,以交织个数为35~90个/m(更优选为40~80个/m)的方式进行了交织加工(交织处理)的纱,则所得织物表面容易形成莲叶状微细凹凸,其结果,容易得到优异的拨水性,因而优选。此外,若复合纱经过这样的交织加工,则织物的织制性能也优异,因而优选。另外,交织加工(交织处理)可以使用通常的交织用喷嘴进行处理。
此外,在上述复合纱中,扭矩越小越好,最好是无扭矩(0T/m)。要形成这样的无扭矩,只要在对具有S方向扭矩的假捻卷缩加工纱和具有Z方向的假捻卷缩加工纱进行合纱时,除了扭矩方向不同以外,使用具有相同扭矩的2种假捻卷缩加工纱即可。
此外,在上述复合纱中,若卷缩率在13%以上(更优选为13~25%),则容易在织物表面形成莲叶状的微细凹凸,从而能得到优异的拨水性,所以优选。该卷缩率小于13%时,存在得不到充分的拨水性之虞。
在上述复合纱中,从在织物表面形成莲叶状的微细凹凸的角度考虑,优选单丝纤度在1dtex以下(更优选为0.001~1.0dtex,进一步优选为0.1~1.0dtex,尤其优选为0.1~0.4dtex)。可以是单丝纤维直径在1μm以下的称作纳米纤维的超极细纤维。若该单丝纤度大于1dtex,则存在得不到充分的拨水性之虞。
此外,作为复合纱的总纤度,优选在33~220dtex的范围内。另外,作为复合纱的单丝根数,从获得优异的拨水性的角度考虑,优选在50根以上(更优选为50~10000根,尤其优选为50~300根)的范围内。
作为构成上述复合纱的纤维,从获得优异的拨水性的角度考虑,优选由聚酯构成的聚酯系纤维。作为这种聚酯,可以列举出以对苯二甲酸为主要酸成分、以选自碳数为2~6的亚烷基二醇为主要二醇成分的聚酯,碳数为2~6的亚烷基二醇为乙二醇、丙二醇、丁二醇、戊二醇、己二醇中的至少1种二醇,尤其优选为乙二醇。
这类聚酯中,可根据需要含有少量(通常在30摩尔%以下)的共聚成分。此时,作为所使用的对苯二甲酸以外的二官能性羧酸,例如可以列举出间苯二甲酸、萘二羧酸、二苯基二羧酸、二苯氧基乙烷二羧酸、β-羟基乙氧基苯甲酸、对羟基苯甲酸、间苯二甲酸-5-磺酸钠、己二酸、癸二酸、1,4-环己烷二羧酸之类的芳香族、脂肪族、脂环族二官能性羧酸。此外,作为上述二醇以外的二醇化合物,例如可以列举出环己烷-1,4-二甲醇、新戊二醇、双酚A、双酚S之类的脂肪族、脂环族、芳香族二醇化合物及聚氧化烯二醇等。
上述聚酯可通过任意方法合成。以聚对苯二甲酸乙二醇酯为例进行说明,则其可以是通过以下第1阶段的反应和第2阶段的反应制得的聚酯。第1阶段的反应:通过使对苯二甲酸和乙二醇进行直接酯化反应、或使对苯二甲酸二甲酯之类的对苯二甲酸低级烷基酯和乙二醇进行酯交换反应、或者使对苯二甲酸和氧化乙烯反应而生成对苯二甲酸的二醇酯和/或其低聚物。第2阶段的反应:减压下对第1阶段的反应生成物加热,使其缩聚反应,直至达到所希望的聚合度。此外,上述聚酯也可以是物质再生或化学再生的聚酯。此外,上述聚酯还可以是聚乳酸、立体复合型聚乳酸等脂肪族聚酯。
上述聚酯也可根据需要而含有消光剂(二氧化钛)、微孔形成剂(有机磺酸金属盐)、着色防止剂、热稳定剂、阻燃剂(三氧化二锑)、荧光增白剂、着色颜料、防静电剂(磺酸金属盐)、吸湿剂(聚氧化烯二醇)、抗菌剂、其他无机粒子中的1种以上。
在本发明的织物中,在经纱或纬纱的至少一方(优选经纱及纬纱)使用上述复合纱。这里,相对于织物的总重量,优选复合纱的含量在70重量%以上(尤其优选为100重量%)。另外,本发明具有织物组织这一点很重要。对于编织物而言,存在得不到优异的拨水性之虞,因而不适宜。
本发明的拨水性织物例如可通过以下方法制造。首先,使用具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱得到复合纱。此时,作为复合方法,可以是交织加工、塔斯纶(Taslan,注册商标)加工等空气混纤、复合假捻、合捻、包覆加工(covering)等任一种。其中,从在织物表面形成莲叶状的微细凹凸、得到拨水性的角度考虑,优选上述交织加工(交织处理)。
接着,使用该复合纱织制织物。此时,对织物的组织无特殊限制。例如,可以列举出平织、斜纹织、锻织等三原组织、变化组织、经二重织、纬二重织等单二重组织、经天鹅绒等。层数可以是单层,也可以是2层以上的多层。此外,织制方法可以是使用通常的织机(例如通常的喷水式织机、喷气式织机、剑杆式织机等)的通常的织制方法。
接着,对该织物实施拨水加工。这里,如上述那样,使用每1g拨水剂中的全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)的合计浓度为0~5ng/g(优选为0ng/g)的氟系拨水剂。优选根据需要而混合防静电剂、三聚氰胺树脂、催化剂,制成拨水剂浓度为3~15重量%左右的加工剂,以50~90%左右的浸吸率使用该加工剂对织物表面进行处理。作为用加工剂对织物表面进行处理的方法,可以列举出轧染法(padding method)、喷雾法等。其中,从使加工剂渗透至织物内部的角度考虑,优选轧染法。上述浸吸率是指相对于织物(施用加工剂前)重量的加工剂的重量比例(%)。
另外,作为上述防静电剂,优选含有聚乙二醇基的聚酯系树脂、含有聚乙二醇基的聚氨酯系树脂、含有聚乙二醇基的聚阳离子系化合物与二缩水甘油醚的反应物等。也可以是高级醇硫酸酯盐、硫酸化油、磺酸盐、磷酸酯盐等阴离子系表面活性剂、胺盐型、季铵盐、咪唑啉型季铵盐等阳离子系表面活性剂、聚乙二醇型、多价醇酯型等非离子系表面活性剂、咪唑啉型季盐、丙氨酸型、甜菜碱型等两性表面活性剂等防静电性化合物。
用于单体聚合的热处理优选为在50~180℃的温度下、在0.1~30分钟的条件下进行干热处理和湿热处理中的至少一种处理。可以是蒸热处理。在该蒸热处理中,优选使用80~160℃的饱和水蒸气或过热水蒸气。此时,作为处理时间,优选在数秒到数十分钟的范围内。进行该烝热处理后,可根据需要进行水洗、热水洗或还原清洗。
此外,若在上述拨水加工工序的前面的工序和后面的工序中的至少一方工序中对织物实施轧光加工,则织物表面容易形成莲叶状,获得优异的拨水性,因而优选。此时,作为轧光加工的条件,优选温度在130℃以上(更优选为140~195℃)、线压在200~20000N/cm(更优选为200~1000N/cm)的范围内。
此外,也可在上述拨水加工工序的前面的工序和后每的工序中的至少一方进行常法的染色加工、碱减量加工、起毛加工。还可加入并施用紫外线遮蔽剂、抗菌剂、除臭剂、防虫剂、蓄光剂、回反射剂、负离子产生剂等
在该织物中,若用下式定义的织物覆盖系数CF在1500~2800的范围内,则能得到更优异的拨水性,因而优选。CF=(DWp/1.1)1/2×MWp+(DWf/1.1)1/2×MWf
其中,DWp为经纱总纤度(dtex),MWp为经纱织造密度(根/2.54cm),DWf为纬纱总纤度(dtex),MWf为纬纱织造密度(根/2.54cm)。
此外,在该织物中,若按JIS L1018测得的织物的膨松性在1.30以上(更优选为1.50~2.00),则能获得更优异的拨水性,因而优选。
在这样所得的拨水性织物中,由于附着有全氟辛酸和全氟辛烷磺酸的合计浓度为0~5ng/g的氟系拨水剂,因此,该拨水性织物成为环保织物。此外,同时,上述复合纱织入在织物中,由此,在该拨水性织物的表面形成莲叶状的微细凹凸。并且,由于该莲叶状的微细凹凸而形成有微小的空气层,因此,在水滴滴到织物表面时,呈现出优异的拨水性。另外,该效果有时也称作莲花效应(lotus effect)。
此时,作为拨水性,织物的拨水滚动角度优选在25度以下(更优选在22度以下,尤其优选为5~22度)。
其中,拨水滚动角度是指在安装在水平板上的平面状的测定用试料上轻轻地滴加0.2cc的水,等速地、轻轻地倾斜该平板、使水滴开始滚动时的角度。
接着,本发明的衣料是使用上述织物制成的衣料。由于使用上述织物,因此,本发明的衣料是环保衣料,而且具有优异的拨水性。该衣料包括羽绒衣料、羽毛球衫、跑步衫、足球裤、网球裤、篮球裤、乒乓球裤、羽毛球裤、跑步裤、高尔夫裤、各种运动用汗衫、各种运动用内衣、毛衣、T恤、针织套衫、运动套装、风衣、夹克等。
另外,由于上述织物是环保织物,且具有优异的拨水性,因此,不仅能良好地用作衣料,还可良好地用作伞布、雨衣布、鞋、帽子、被套、被罩等。
实施例
接着对本发明的实施例和比较例进行详述,但本发明并不局限于此。另外,实施例中的各测定项目用下述方法进行了测定。
(1)扭矩
将约70cm的试料(卷缩纱)横向拉开,在中央部吊上0.18mN×标示特克斯(2mg/de)的初始荷载后,将两端并拢。
纱因残留扭矩而开始旋转,保持该状态直至旋转停止,得到捻纱。对这样得到的捻纱在17.64mN×标示特克斯(0.2g/de)的荷载下用检捻器测定25cm长度的捻数。将所得捻数(T/25cm)乘以4倍,算出扭矩(T/m)。
(2)交织个数
在8.82mN×标示特克斯(0.1g/de)的荷载下取1m长的交织纱,去除荷载后,读取在室温下放缩24小时后的节点的数目,用个/m表示。
(3)卷缩率
将测试用纱条卷绕在周长为1.125m的检尺机周围,调制成干纤度为3333dtex的绞纱。将上述绞纱悬挂在刻度板的吊钉上,在其下部施加6g的初始荷载,测定再施加600g荷载时的绞纱的长度L0。之后,立即从上述绞纱上除去荷载,从刻度板的吊钉上取下绞纱,将该绞纱在沸水中浸渍30分钟,使其卷缩。将沸水处理过的绞纱从沸水中取出,用滤纸吸除绞纱中所含的水分,在室温下风干24小时。将该风干后的绞纱悬挂在刻度板的吊钉上,在其下部加载600g的荷载,1分钟后测定绞纱的长度L1a,之后,从绞纱上卸下荷载,1分钟后测定绞纱的长度L2a。由下式算出测试用单丝纱条的卷缩率(CP)。
CP(%)=((Lla-L2a)/L0)×100
(4)拉伸性
按JISL1096B法测定了拉伸性(%)。
(5)织物的厚度
按JIS L1096测定了织物的厚度(mm)。
(6)织物的基重
按JIS L1096测定了织物的基重(g/m2)。
(7)织物的膨松性
按JIS L1018测定了织物的膨松性。
(8)覆盖系数
通过下式CF求出了织物的覆盖系数。
CF=(DWp/1.1)1/2×MWp+(DWf/1.1)1/2×MWf
其中,DWp为经纱总纤度(dtex),MWp为经纱织造密度(根/2.54cm),DWf为纬纱总纤度(dtex),MWf为纬纱织造密度(根/2.54cm)。
(9)拨水性(拨水滚动角度)
向安装在水平板上的平面状的测定用试料上轻轻地滴加0.2cc的水,等速地、轻轻地倾斜该平板,将水滴开始滚动时的角度作为拨水滚动角度。拨水滚动角度越小,拨水性越良好,以25度以下为合格。
(10)PFOA和PFOS的浓度
在以下条件下测定PFOA和PFOS的浓度,用ng/g表示。
装置:LC-MS/MS串联质谱仪TSQ-7000(ThermoElectron公司产品)
高效液相色谱LC-10Avp(岛津制作所产品)
色谱柱:Capcellpak C8100mm×2mmi.d.(5μm)
流动相:A:0.5mmol/L醋酸铵,B:乙腈
流速:0.2mL/min
试料注入量:3μL
CP温度:220℃
离子化电压:4.5kv
IonMulti:1300v
离子化法:ESI-Negative
实施例1
使用聚对苯二甲酸乙二醇酯,由通常的纺纱装置在280℃进行熔融纺纱,以2800m/分的速度拉取,在不拉伸的情况下进行卷取,得到56dtex/36fil的半延伸聚对苯二甲酸乙二醇酯纱条。
接着,使用该对苯二甲酸乙二醇酯纱条,在拉伸倍率为1.6倍、假捻数为2500T/m(S方向)、加热箱温度为180℃、纱速为350m/分钟的条件下进行同时拉伸假捻卷缩加工。
此外,使用上述聚对苯二甲酸乙二醇酯砂条,在拉伸倍率为1.6倍、假捻数为2500T/m(Z方向)、加热箱温度为180℃、纱速为350m/分钟的条件下进行同时拉伸假捻卷缩加工。
接着,将这些具有S方向扭矩的假捻卷缩加工纱和Z方向的假捻卷缩加工纱合纱,进行交织加工(交织处理),得到复合纱(66dtex/72fil,卷缩率为16%,扭矩为0T/m)。交织加工中使用交织用喷嘴,在超喂率为1.0%、压缩空气压力为0.3MPa(3kgf/cm2)下形成50个/m的交织。
接着,将该复合纱用在经纱和纬纱中,并使用通常的喷水式织机织成平纹组织的织物(仅由上述复合纱构成的织物)。
接着,使用U-Sofcer(松弛整理机)在95℃的温度下对上述织物进行开幅精炼,然后,使用液流染色机在120℃的温度下进行松弛处理。接着,使用拉幅机在190℃的温度下对该织物进行中间定型。再使用液流染色机在130℃的温度下用分散染料进行染色加工,然后,实施下述拨水加工。
拨水加工使用下述加工剂,以80%的浸吸率进行榨液,在130℃下干燥3分钟后,在170℃下热处理45秒。
<加工剂组成>
·氟系拨水剂8.0重量%
(旭硝子公司产品,AsahiGuard E系列AG-E061PFOA:小于1ng/g,PFOS:小于1ng/g)
·三聚氰胺树脂0.3重量%
(住友化学公司产品,Sumitex Resin M-3)
·催化剂0.3重量%
(住友化学公司产品,Sumitex Accelerator ACX)
·水91.4重量%
接着,使用拉幅机在170℃的温度下对该织物进行最终定型。然后,在辊温度为150℃、线压为300N/cm下对该织物进行轧光加工,得到拨水性织物。
这样所得的拨水性织物的厚度为0.15mm,基重为92g/m2,膨松性为1.67,经向密度为132根/2.54cm,纬向密度为112根/2.54cm,覆盖系数为1890,纬向拉伸性为7%,滚动角度为18度。在该拨水性织物的表面形成有莲叶状的微细凹凸,该拨水性织物的拨水性优异。此外,由于该拨水性织物上附着有上述拨水剂,因此,该拨水性织物是环保的织物。
使用该拨水性织物缝制风衣(运动衣料),试验者试穿该风衣后发现,该风衣的拨水性优异。
比较例1
除了在实施例1中将聚对苯二甲酸乙二醇酯的假捻卷缩加工纱(56dtex/72fil,卷缩率为14%,扭矩为45T/m)不是制成复合纱,而是作为单独的纱用在经纱和纬纱中以外,按与实施例1相同的方法进行操作。
所得的拨水性织物的厚度为0.09mm,基重为75g/m2,膨松性为1.16,经向密度为148根/2.54cm,纬向密度为120根/2.54cm,覆盖系数为1900,纬向拉伸性为4%,滚动角度为26度。虽然该拨水性织物是环保织物,但拨水性差。
使用该织物缝制风衣(运动衣料),试验者试穿该风衣后发现,该风衣的拨水性差。
根据本发明,可得到环保的、具有优异拨水性的拨水性织物及使用该拨水性织物制成的衣料,其工业价值极大。

Claims (11)

1.拨水性织物,其附着有全氟辛酸和全氟辛烷磺酸的合计浓度为0~5ng/g的氟系拨水剂,包含有含具有S方向扭矩的假捻卷缩加工纱和具有Z方向扭矩的假捻卷缩加工纱的复合纱。
2.根据权利要求1所述的拨水性织物,其特征在于,构成所述复合纱的纤维的单丝纤度在1dtex以下。
3.根据权利要求1所述的拨水性织物,其特征在于,所述复合纱的单丝根数在50根以上。
4.根据权利要求1所述的拨水性织物,其特征在于,所述复合纱的卷缩率在13%以上。
5.根据权利要求1所述的拨水性织物,其特征在于,所述复合纱经过交织加工,交织个数为35~90个/m。
6.根据权利要求1所述的拨水性织物,其特征在于,织物的覆盖系数在1500~2800的范围内。
7.根据权利要求1所述的拨水性织物,其特征在于,织物经过轧光加工。
8.根据权利要求1所述的拨水性织物,其特征在于,织物表面形成有莲叶状微细凹凸。
9.根据权利要求1所述的拨水性织物,其特征在于,按JIS L1018测得的织物的膨松性在1.30以上。
10.根据权利要求1所述的拨水性织物,其特征在于,织物的拨水滚动角度在22度以下。
11.衣料,其用权利要求1~9中任一项所记载的拨水性织物制成。
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KR20130137661A (ko) 2013-12-17
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EP2650430B1 (en) 2018-03-14
TW201229343A (en) 2012-07-16
ES2664474T3 (es) 2018-04-19
JPWO2012077488A1 (ja) 2014-05-19
EP2650430A4 (en) 2017-03-08
EP2650430A1 (en) 2013-10-16
US9127380B2 (en) 2015-09-08
CN103298993B (zh) 2015-11-25
WO2012077488A1 (ja) 2012-06-14
TWI593842B (zh) 2017-08-01
JP5698262B2 (ja) 2015-04-08
US20130239289A1 (en) 2013-09-19

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