CN113423771B - 用于柔性显示器的窗口膜 - Google Patents
用于柔性显示器的窗口膜 Download PDFInfo
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- CN113423771B CN113423771B CN202080014476.4A CN202080014476A CN113423771B CN 113423771 B CN113423771 B CN 113423771B CN 202080014476 A CN202080014476 A CN 202080014476A CN 113423771 B CN113423771 B CN 113423771B
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- low refractive
- film
- window film
- flexible display
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Classifications
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- G—PHYSICS
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Abstract
本发明提供一种用于柔性显示器的窗口膜,其即使使用具有高黄度指数的聚酰亚胺膜,也能够通过将整个窗口膜的颜色调节为中性而具有高透射率和低黄度指数。此外,本发明涉及一种包括该窗口膜的光学层叠体和一种图像显示装置。
Description
技术领域
本发明涉及一种用于柔性显示器的窗口膜、包括该窗口膜的光学层叠体和显示装置。更具体地,本发明涉及一种用于柔性显示器的窗口膜、包括该窗口膜的光学层叠体和显示装置,所述用于柔性显示器的窗口膜即使使用具有高黄度指数的聚酰亚胺膜,也能够通过将整个窗口膜的颜色调节为中性而具有高透射率和低黄度指数。
背景技术
近来,已经积极开发了能够显示包含图像的信息的显示装置。显示装置包括液晶显示(LCD)装置、有机发光显示(OLED)装置、等离子显示面板(PDP)装置和场致发射显示(FED)装置等。
在显示装置中,用于保护显示面板免受外部环境影响的窗口基板或窗口膜可以设置在诸如LCD面板和OLED面板的显示面板上。窗口基板或窗口膜可包括由玻璃材料制成的基底基板,并且随着近来开发出柔性显示器,已将透明塑料材料用作基底基板。
为了替代用于柔性显示器的传统的窗口盖玻璃,透明塑料薄膜应满足高硬度和光学性能。
聚酰亚胺(PI)是一种高性能聚合物材料,具有高的热稳定性、机械性能、耐化学性和电性能,并且作为用于柔性显示器的基板材料已越来越受到关注。然而,由于聚酰亚胺膜的黄度指数较高,当应用于需要透明性的窗口膜时应加以修正。
韩国专利申请公开第2018-0089860号公开了一种聚酰亚胺膜,其含有至少一种上蓝剂以修正聚酰亚胺膜的黄度指数。然而,聚酰亚胺膜存在由于上蓝剂的加入导致整个膜的透射率降低的问题。
发明内容
【技术问题】
本发明的目的是提供一种用于柔性显示器的窗口膜,其即使使用具有高黄度指数的聚酰亚胺膜,也能够通过将整个窗口膜的颜色调节为中性而具有高透射率和低黄度指数。
本发明的另一个目的是提供一种包含用于柔性显示器的窗口膜的光学层叠体。
本发明的又一个目的是提供一种具有该光学层叠体的显示装置。
【技术方案】
根据本发明的一个方面,提供一种用于柔性显示器的窗口膜,其包括聚酰亚胺膜和在聚酰亚胺膜的至少一个表面上的低折射层,其中所述低折射层的折射率低于所述聚酰亚胺膜的折射率,
其中窗口膜满足以下数学式1至3:
【数学式1】
A-B≤0.55(%)
【数学式2】
黄度指数(YI)≤2.0
【数学式3】
绿光透射率(Y)≥92%
其中,
A是540nm处的透射率(%),并且
B是480nm处的透射率(%)。
在本发明的一个实施方式中,聚酰亚胺膜的黄度指数(YI)可以超过2.0。
在本发明的一个实施方式中,低折射层的折射率为1.5或更小,优选地,可以在聚酰亚胺膜的折射率的正平方根-0.1至聚酰亚胺膜的折射率的正平方根+0.2的范围内。
在本发明的一个实施方式中,低折射层的厚度可以在30nm至130nm/(低折射层的折射率)的范围内。
在本发明的一个实施方式中,低折射层可由包含低折射材料、透光树脂、光引发剂和溶剂的低折射层形成组合物形成。
在本发明的一个实施方式中,低折射材料可以包括中空二氧化硅纳米颗粒。
在本发明的一个实施方式中,用于柔性显示器的窗口膜还可以包括在聚酰亚胺膜和低折射层之间的硬涂层。
根据本发明的另一方面,提供一种光学层叠体,其包括用于柔性显示器的窗口膜;和光学层,所述光学层层叠在所述用于柔性显示器的窗口膜的一个表面上。
在本发明的一个实施方式中,光学层可以包括偏光板和触摸传感器中的至少一者。
根据本发明的另一方面,提供一种具有所述光学层叠体的显示装置。
【有益效果】
根据本发明的用于柔性显示器的窗口膜即使使用黄度指数(YI)超过2.0的聚酰亚胺膜,也能够通过将整个窗口膜的颜色调节为中性而具有低黄度指数(YI),并且还由于低折射层的减反射作用而具有高透射率。
附图说明
图1示出了根据实施例和比较例的窗口膜和聚酰亚胺膜的透射光谱。
具体实施方式
在下文中,将更详细地描述本发明。
本发明的一个实施方式涉及一种用于柔性显示器的窗口膜,其包括聚酰亚胺膜和在聚酰亚胺膜的至少一个表面上的低折射层,其中低折射层的折射率低于聚酰亚胺膜的折射率,
其中所述窗口膜满足以下数学式1至3:
【数学式1】
A-B≤0.55(%)
【数学式2】
黄度指数(YI)≤2.0
【数学式3】
绿光透射率(Y)≥92%
其中,
A是540nm处的透射率(%),并且
B是480nm处的透射率(%)。
黄度指数(YI)是表示黄度程度的指数,是根据分光光度数据计算出的值,分光光度数据将测试样品的颜色描述为透明或白色(低YI)到黄色(高YI)。在本文中,黄度指数可以根据ASTM E313-73中描述的方法测量。
绿色光透射率(Y)是根据CIE 1931从测量可见光区域的透射率计算的值。在本文中,绿光透射率(Y)可以通过分光光度计测量,具体可以按照后述的实验例中所示的方法测量。
在本发明的一个实施方式中,最大化蓝色区域的相消干涉以提高蓝色区域的透射率并满足数学式1,即,将540nm处的透射率(A)与480nm(B)处的透射率之差(A-B)控制为0.55%或更小,从而可以补偿聚酰亚胺膜基板本身的低蓝色区域透射率。因此,根据本发明的一个实施方式的窗口膜即使使用具有黄度指数(YI)超过2.0的聚酰亚胺膜,也可以通过将整个窗口膜的颜色调节为中性而具有低黄度指数(YI),并且还由于低折射层的减反射作用而具有高透射率。
在本发明的一个实施方式中,540nm处的透射率(A)与480nm处的透射率(B)的差值(A-B)、黄度指数和绿光透射率可以通过调节折射率和低折射层的厚度来控制。
在本发明的一个实施方式中,低折射层是折射率低于聚酰亚胺膜的折射率的层,并且该层形成未使得低折射层表面上的反射光和低折射层与聚酰亚胺膜之间的界面上的反射光低会导致彼此相消干涉。
低折射层的折射率可以为1.5或更小,以引起有效的薄膜干涉,优选地,可以在聚酰亚胺膜的折射率的正平方根-0.1至聚酰亚胺膜的折射率的正平方根+0.2的范围内,并且更优选地,可以在聚酰亚胺膜的折射率的正平方根-0.05至聚酰亚胺膜的折射率的正平方根+0.15的范围内。当低折射层的折射率超出上述范围时,相消干涉性能可能会降低。特别地,当低折射层的折射率低于上述下限时,低折射层的机械性能可能会劣化。
在本发明的一个实施方式中,低折射层的厚度可以为30nm至130nm/(低折射层的折射率),以最大化蓝光区域的相消干涉效应。当低折射层的厚度小于30nm时,在紫外区相消干涉最大化,因此在蓝光区域相消干涉作用很小。当厚度超过130nm/(低折射层的折射率)时,相消干涉在600nm或更高的区域达最大化,使得在绿光或红光区域的透射率可以大大增加。在这种情况下,涂膜的黄度指数会大大增加,从而使膜看起来发黄。
根据本发明的一个实施方式的用于柔性显示器的窗口膜包括聚酰亚胺膜和在聚酰亚胺膜的至少一个表面上的低折射层,其中低折射层的折射率低于聚酰亚胺膜的折射率。
在本发明的一个实施方式中,聚酰亚胺膜用作窗口膜的基底。
聚酰亚胺膜的黄度指数(YI)超过2.0,可以商购或制备使用。
聚酰亚胺膜的厚度没有特别限定,例如可以为30-100μm,优选为40-80μm。当聚酰亚胺膜的厚度小于30μm时,对下层的保护性能可能劣化并且可能难以处理。当厚度超过100μm时,弯曲性能可能会降低。
在本发明的一个实施方式中,可以通过在聚酰亚胺膜上涂布低折射层形成的组合物来形成低折射层。
在本发明的一个实施方式中,形成低折射层的组合物可包含低折射材料、透光树脂、光引发剂和溶剂。
在本发明的一个实施方式中,低折射材料可以具有1.5或更小的折射率,其典型示例可以包括含氟材料如MgF2、中空纳米颗粒如中空二氧化硅纳米颗粒和硅系材料。
低折射材料的含量没有特别限制,但基于100重量份的低折射层形成组合物的总量可以为1-80重量份。当低折射材料的量小于1重量份时,降低折射率的效果可能很小,而当低折射材料的量超过80重量份时,机械性能可能劣化。
在本发明的一个实施方式中,透光树脂为光固化性树脂。光固化性树脂可包括光固化(甲基)丙烯酸酯低聚物和/或单体。
作为光固化性(甲基)丙烯酸酯低聚物,通常使用环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等,优选氨基甲酸酯(甲基)丙烯酸酯。氨基甲酸酯(甲基)丙烯酸酯可以通过使分子中具有羟基的多官能(甲基)丙烯酸酯与具有异氰酸酯基的化合物在催化剂的存在下反应来制备。分子中具有羟基的多官能(甲基)丙烯酸酯的具体示例可包括选自由(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基异丙酯、(甲基)丙烯酸4-羟基丁酯、己内酯开环羟基丙烯酸酯、季戊四醇三/四(甲基)丙烯酸酯混合物和二季戊四醇五/六(甲基)丙烯酸酯混合物组成的组中的至少一种。具有异氰酸酯基的化合物的具体示例可包括选自由1,4-二异氰酸酯基丁烷、1,6-二异氰酸酯基己烷、1,8-二异氰酸酯基辛烷、1,12-二异氰酸酯基十二烷、1,5-二异氰酸酯基-2-甲基戊烷、三甲基-1,6-二异氰酸酯基己烷、1,3-双(异氰酸甲酯基)环己烷、反式-1,4-环己烯二异氰酸酯、4,4'-亚甲基双(环己基异氰酸酯)、异佛尔酮二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、二甲苯-1,4-二异氰酸酯、四甲基二甲苯-1,3-二异氰酸酯、1-氯甲基-2,4-二异氰酸酯、4,4'-亚甲基双(2,6-二甲基苯基异氰酸酯)、4,4'-氧双(苯基异氰酸酯)、衍生自六亚甲基二异氰酸酯和甲苯二异氰酸酯的三甲丙醇加合物的三官能异氰酸酯组成的组中的至少一种。
作为单体,可以使用本领域常用的任何单体而没有限制,但是具有不饱和基团例如(甲基)丙烯酰基、乙烯基、苯乙烯基和烯丙基作为可光固化官能团的单体是优选的,具有(甲基)丙烯酰基的单体是更优选的。
具有(甲基)丙烯酰基的单体的具体示例可包括选自由新戊二醇丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基乙烷三(甲基)丙烯酸酯、1,2,4-环己烷四(甲基)丙烯酸酯、五甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇三(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、双(2-羟基乙基)异氰脲酸酯二(甲基)丙烯酸酯、(甲基)丙烯酸羟基乙酯、(甲基)丙烯酸羟基丙酯、(甲基)丙烯酸羟基丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸苯氧基乙酯和(甲基)丙烯酸异冰片酯组成的组中的至少一种。
作为透光树脂例示的光固化性(甲基)丙烯酸酯低聚物和单体可以单独使用或以两种或更多种组合使用。
基于100重量份的低折射层形成组合物的总量,透光树脂的含量可以为但不限于1-80重量份。当该量小于1重量份时,难以获得足够的硬度改善,并且当超过80重量份时,存在卷曲严重的问题。
在本发明的一个实施方式中,光引发剂可以不受限制地使用,只要它是本领域中使用的即可。例如,可以使用选自由羟基酮、氨基酮、夺氢型光引发剂及其组合组成的组中的至少一种。
具体地,光引发剂可以包括选自由2-甲基-1-[4-(甲硫基)苯基]2-吗啉丙酮-1、二苯基酮、苄基二甲基缩酮、2-羟基-2-甲基-1-苯基-酮、4-羟基环苯基酮、二甲氧基-2-苯基苯乙酮、蒽醌、芴、三苯胺、咔唑、3-甲基苯乙酮、4-氯苯乙酮、4,4-二甲氧基苯乙酮、4,4-二氨基二苯甲酮、1-羟基环己基苯基酮、二苯甲酮、二苯基(2,4,6-三甲基苯甲酰基)氧化膦,及其组合组成的组中的至少一种。
基于100重量份的低折射层形成组合物的总量,光引发剂的含量可以为0.1-10重量份,优选1-5重量份。如果光引发剂的量小于0.1重量份,则组合物的固化速率可能低并且一些部分可能未固化,使得机械性能可能劣化。如果该量超过10重量份,则由于过度固化而在涂膜中可能出现裂纹。
在本发明的一个实施方式中,可以使用溶剂而没有限制,只要它是本领域已知的能够溶解或分散上述组合物的溶剂。
溶剂的优选示例可以包括醇(甲醇、乙醇、异丙醇、丁醇、甲基溶纤剂、乙基溶纤剂等)、酮(甲基乙基酮、甲基丁基酮、甲基异丁基酮、二乙基酮、二丙基酮、环己酮等)、乙酸酯(乙酸乙酯、乙酸丙酯、乙酸正丁酯、乙酸叔丁酯、乙酸甲基溶纤剂、乙酸乙基溶纤剂、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单丙醚乙酸酯、乙酸甲氧基丁酯、乙酸甲氧基戊酯等)、己烷(己烷、庚烷、辛烷等)、苯(苯、甲苯、二甲苯等)、醚(二甘醇二甲醚、二甘醇二乙醚、二甘醇二丙醚、二甘醇二丁醚、丙二醇单甲醚等)等。上述例示的溶剂可以单独使用或以两种或更多种的组合使用。
基于100重量份的低折射层形成组合物的总量,溶剂的含量可以为10-95重量份。如果溶剂的量小于10重量份,则粘度可能增加从而劣化可加工性。如果该量超过95重量份,则存在干燥过程可能需要很长时间并且可能降低经济效率的缺点。
在本发明的一个实施方式中,除上述组分外,低折射层形成组合物还可包含本领域常用的其他组分,例如抗氧化剂、紫外线吸收剂、光稳定剂、热阻聚剂、流平剂、表面活性剂、润滑剂、防污剂等。
低折射层可以通过在聚酰亚胺膜的一个表面或两个表面上涂布低折射层形成组合物,然后进行干燥和UV固化来形成。
低折射层形成用组合物的涂覆过程可以通过适当使用诸如模涂机、气刀、反转辊、喷涂、刮刀、流延、凹版印刷、微凹版印刷、旋涂等公知的方法进行。
在将低折射层形成组合物涂覆在聚酰亚胺膜上之后,可以通过在30-150℃的温度蒸发挥发物10秒至1小时,更具体地30秒至30分钟来进行干燥过程,然后,可以通过紫外线照射进行固化过程。特别地,紫外线的照射量可以为约0.01-10J/cm2,更特别地为0.1-2J/cm2。
根据本发明的一个实施方式的窗口膜还可以包括在聚酰亚胺膜和低折射层之间的硬涂层以提高机械强度。
在还包括硬涂层的情况下,窗口膜可以按照聚酰亚胺膜/硬涂层/低折射层的顺序层叠。
此外,还可以在聚酰亚胺膜的背面层叠硬涂层和/或低折射层。在这种情况下,窗口膜可以按照硬涂层/聚酰亚胺膜/硬涂层/低折射层,或低折射层/硬涂层/聚酰亚胺膜/硬涂层/低折射层的顺序层叠。
硬涂层可具有额外的抗静电性能等。
本发明的一个实施方式涉及一种光学层叠体,其包括用于柔性显示器的窗口膜和层叠在用于柔性显示器的窗口膜的一个表面上的光学层。
光学层可以包括偏光板和触摸传感器中的至少一者。
在本发明的一种实施方式中,偏光板可以包括偏光器,并且如果需要,可以包括层叠在偏光器的至少一个表面上的保护膜。
另外,触摸传感器可以是如下触摸传感器:在载体基板上形成分离层以进行触摸传感器形成工艺,当与载体基板分离时,分离层用作布线覆盖层。例如,触摸传感器可以是具有膜形状的薄膜触摸传感器。
本发明的一个实施方式涉及一种具有上述光学层叠体的显示装置。
根据本发明的一个实施方式的显示装置具有附接在显示面板的一个表面上的光学层叠体。
显示装置的类型没有特别限制,但其示例可以包括液晶显示装置、有机EL显示装置、等离子显示装置、场发射显示装置、阴极射线管显示装置等。
显示面板没有特别限制,可以具有本领域常用的元件。此外,其还可以包括本领域常用的其他元件。
在下文中,将参考实施例、比较例和实验例更详细地描述本发明。本领域技术人员应当清楚,这些实施例、比较例和实验例仅用于说明目的,本发明的范围不限于此。
制备例1:低折射层形成组合物的制备
将2重量份的二季戊四醇六丙烯酸酯、6重量份的中空二氧化硅(JGC C&C,THRULYA4320,固含量20%)、0.5重量份的光引发剂(BASF,Irgacure 184)、91.2重量份的丙二醇和0.3重量份的流平剂(BYK,BYK-UV3570)混合以制备低折射层形成组合物。
低折射率形成组合物固化后的折射率为1.35。
实施例1-3和比较例1-3:窗口膜的制备
使用下表1中列出的每个meyer棒式涂布机将制备实施例1中获得的低折射率层形成组合物涂覆在40μm透明聚酰亚胺膜(Sumitomo Chemical Co.,Ltd.,YI 2.33,折射率:1.54)上,然后在90℃干燥3分钟。然后,在氮气吹扫下,使用高压汞灯以600mJ/cm2的UV进行照射以形成具有下表1所示的各干燥厚度的低折射层以制备窗口膜。
【表1】
Meyer棒# | 干厚度(nm) | |
实施例1 | 4 | 70 |
实施例2 | 5 | 80 |
实施例3 | 3 | 60 |
比较例1 | 7 | 110 |
比较例2 | 6 | 100 |
比较例3 | 8 | 125 |
实验例1:
如下测量上述制备的窗口膜的物理性能,结果示于下表2中。
1)透射光谱
使用Konica Minolta积分球分光光度计(CM-3600d)在SCI模式下测量制备的窗口膜的透射光谱。结果示于图1。计算540nm处的透射率(A)与480nm处的透射率(B)的差值(A-B)。
2)黄度指数(YI)
使用Konica Minolta积分球分光光度计(CM-3600d)在SCI模式下使用ASTM E313-73标准方法测量制备的窗口膜的黄度指数。
3)绿光透射率(Y)
使用Konica Minolta积分球分光光度计(CM-3600d)在SCI模式下测量制备的窗口膜的绿光透射率(Y)。
【表2】
由表2可知,实施例1-3的窗口膜的540nm处的透射率(A)与480nm处的透射率(B)之差(A-B)被调节为0.55%或更小,显示出在蓝光区域中的透射率增加以具有2.0或更小的低黄度指数(YI)。此外,确认了与未涂覆低折射层形成组合物的聚酰亚胺膜相比,其具有增加的绿光透射率(Y),为92%或更高。
另一方面,在其中540nm处的透射率(A)与480nm处的透射率(B)之差(A-B)超过0.55%的比较例1-3的窗口膜以及没有涂覆低折射层形成组合物的聚酰亚胺膜的情况下,在蓝光区域出现陡峭的斜率,导致超过2.0的高黄度指数(YI)。
虽然已经详细描述了本发明的具体部分,但是对于本领域技术人员来说,显然这些具体描述仅仅是优选实施方式,本发明的范围并不限于此。此外,本领域技术人员应理解,基于以上描述,可以在不脱离本发明的范围的情况下进行各种应用和修改。
因此,本发明的实质范围由所附权利要求及其等同方案来限定。
Claims (10)
1.一种用于柔性显示器的窗口膜,包括聚酰亚胺膜和在所述聚酰亚胺膜的至少一个表面上的低折射层,其中所述低折射层的折射率低于所述聚酰亚胺膜的折射率,
其中所述低折射层的厚度在30nm至130nm/(所述低折射层的所述折射率)的范围内,
其中所述窗口膜满足以下数学式1至3:
【数学式1】
A-B≤0.55(%)
【数学式2】
黄度指数(YI)≤2.0
【数学式3】
绿光透射率(Y)≥92%
其中,
A是540nm处的透射率(%),并且
B是480nm处的透射率(%)。
2.根据权利要求1所述的用于柔性显示器的窗口膜,其中所述聚酰亚胺膜的黄度指数(YI)超过2.0。
3.根据权利要求1所述的用于柔性显示器的窗口膜,其中所述低折射层的折射率为1.5或更小。
4.根据权利要求3所述的用于柔性显示器的窗口膜,其中所述低折射层的所述折射率在所述聚酰亚胺膜的折射率的正平方根-0.1至所述聚酰亚胺膜的折射率的正平方根+0.2的范围内。
5.根据权利要求1所述的用于柔性显示器的窗口膜,其中所述低折射层由包含低折射材料、透光树脂、光引发剂和溶剂的低折射层形成组合物形成。
6.根据权利要求5所述的用于柔性显示器的窗口膜,其中所述低折射材料包括中空二氧化硅纳米粒子。
7.根据权利要求1所述的用于柔性显示器的窗口膜,还包括在所述聚酰亚胺膜与所述低折射层之间的硬涂层。
8.一种光学层叠体,包含:根据权利要求1-7中任一项所述的用于柔性显示器的窗口膜;和光学层,所述光学层层叠在所述用于柔性显示器的窗口膜的一个表面上。
9.根据权利要求8所述的光学层叠体,其中所述光学层包括偏光板和触摸传感器中的至少一者。
10.一种显示装置,具有根据权利要求8所述的光学层叠体。
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PCT/KR2020/001895 WO2020166933A1 (ko) | 2019-02-15 | 2020-02-11 | 플렉시블 디스플레이용 윈도우 필름 |
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TWI435902B (zh) * | 2007-08-20 | 2014-05-01 | Kolon Inc | 聚亞醯胺膜 |
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