CN103282416B - 聚酰亚胺薄膜的制备方法 - Google Patents
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Abstract
本发明涉及一种通过卷对卷法制备聚酰亚胺薄膜的方法,更具体而言,涉及一种在聚酰亚胺薄膜的制造过程中通过退火过程制备具有优异的光学各向同性的聚酰亚胺薄膜的方法。
Description
技术领域
本发明涉及制备具有低的双折射率和优异的光学各向同性的透明聚酰亚胺薄膜的方法。
背景技术
通常,聚酰亚胺(PI)薄膜由聚酰亚胺树脂形成。此处,聚酰亚胺树脂为通过包括以下步骤的过程制备的高耐热性树脂:使芳族二酐与芳族胺或芳族二异氰酸酯进行溶液聚合以得到聚酰胺酸衍生物;使聚酰胺酸衍生物在高温下关环并脱水以使该聚酰胺酸衍生物亚胺化。
这种不熔化的超高耐热性树脂聚酰亚胺树脂,由于具有优异的耐氧化性、耐热性、耐辐射性、低温特性、耐化学性等性能,已经广泛用于例如汽车材料、航空材料和宇宙飞船材料等的高科技耐热材料领域,以及例如绝缘涂层剂、绝缘薄膜、半导体和TFT-LCD的电极保护膜等的电子材料领域。近来,聚酰亚胺树脂还已经用于例如光纤维和液晶取向膜等显示材料,并且通过向聚酰亚胺树脂添加导电填料或在聚酰亚胺膜的表面上涂布导电填料而已经用于透明电极薄膜。
但是,聚酰亚胺树脂具有如下问题:由于其高的芳香环密度而呈现褐色或黄色,所以在可见光范围内其透明度低;由于其呈现黄色而透光率低;以及由于其具有高的双折射率而难以用作光学材料。
为了解决这个问题,已经尝试了对单体和溶剂进行精制然后对精制的单体进行聚合的方法,但是这种方法的问题是透光率没有得到太大的改善。
美国专利号5053480公开了使用脂族环二酐代替芳族二酐来制备聚酰亚胺树脂的方法。这种方法的优点在于,当通过这种方法制备的聚酰亚胺树脂形成溶液相或薄膜时,其透明度和颜色得到改善,但问题在于,其透明度的改善是有限的,因此不能得到满意的透明度,并且其热性能和机械性能劣化。
此外,美国专利号4595548、4603061、4645824、4895972、5218083、5093453、5218077、5367046、5338826、5986036和6232428以及韩国未经审查的专利申请公开号2003-0009437报道了一种新型的聚酰亚胺结构,在其热性能没有极大劣化的情况下,通过使用具有在其间位而不是对位与例如-O-、-SO2-、CH2-等官能团连接的弯曲结构的单体、具有例如-CF3等取代基的芳族二酐、以及芳族二胺单体,改善了聚酰亚胺的透光率和颜色透明度。然而,这些专利和专利申请报道该新型聚酰亚胺结构的双折射率是不够的。
而且,为了以工业规模生产聚酰亚胺薄膜,必须采用卷对卷(roll to roll)法。然而,当采用卷对卷法生产聚酰亚胺薄膜时,有一个问题是必须在纵向(machinery direction)(MD)上施加张力,因此由于在生产过程中施加的剪切应力而在膜形成时进行取向,所以聚酰亚胺薄膜难以具有光学各向同性。
发明内容
技术问题
本发明的目的是提供一种采用卷对卷法制备具有低的双折射率和优异的光学各向同性的透明聚酰亚胺薄膜的方法。
技术方案
为了实现上述目的,本发明的一个方面提供一种采用卷对卷法制备聚酰亚胺薄膜的方法,其中,在纵向(MD)的张力为10N以下的条件下,在200~400℃下进行退火200~2000秒。
所述制备聚酰亚胺薄膜的方法可以包括以下步骤:将二酐和二胺溶解在溶剂中并反应以得到聚酰胺酸溶液;将聚酰胺酸溶液浇铸在支撑体上,然后加热至200~400℃保持5~400秒以使该聚酰胺酸溶液亚胺化。
在该方法中,所述溶剂可以为选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)、丙酮和二乙酸乙酯(diethyl acetate)中的至少一种有机溶剂。
此外,所述制备聚酰亚胺薄膜的方法可以包括以下步骤:将二酐和二胺溶解在第一溶剂中并反应以得到聚酰胺酸溶液;使该聚酰胺酸溶液亚胺化;将亚胺化的溶液引入第二溶剂中,然后过滤该亚胺化的溶液并干燥以得到聚酰亚胺树脂固体;将该聚酰亚胺树脂固体溶解在所述第一溶剂中以形成聚酰亚胺溶液;将所述聚酰亚胺溶液浇铸在支撑体上然后干燥该聚酰亚胺溶液。
在该方法中,所述第一溶剂可以为选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)、丙酮、二乙酸乙酯中的至少一种有机溶剂,所述第二溶剂可以为极性比第一溶剂低的溶剂,并且可以为选自水、醇、醚和酮中的至少一种溶剂。
具体实施方式
下面,将详细描述本发明。
本发明提供一种采用卷对卷法制备聚酰亚胺薄膜的方法,其中,在纵向(MD)的张力为10N以下的条件下,在200~400℃下进行退火200~2000秒。
也就是说,在根据本发明的制备聚酰亚胺薄膜的方法中,通过在纵向(MD)的张力为10N以下的条件下,在200~400℃下进行退火过程200~2000秒,可以改善聚酰亚胺薄膜的光学各向同性。
在本发明中,制备聚酰亚胺薄膜的方法可以包括以下步骤:将二酐和二胺溶解在溶剂中并反应以得到聚酰胺酸溶液;将该聚酰胺酸溶液浇铸在支撑体上,然后加热该浇铸的聚酰胺酸溶液至200~400℃保持5~400秒。
所述二酐可以为选自2,2-双(3,4-二羧基苯基)六氟丙烷二酐(FDA)、4-(2,5-二氧代四氢呋喃-3-基)-1,2,3,4-四氢化萘-1,2-二羧酸酐(TDA)和4,4′-(4,4′-亚异丙基二苯氧基)双(邻苯二甲酸酐)(HBDA)中的至少一种芳族二酐。所述二酐还可以包括选自苯均四甲酸二酐(PMDA)、联苯四甲酸二酐(BPDA)、氧二邻苯二甲酸二酐(oxydiphthalic dianhydride,ODPA)和1,1’-双环己烷-3,4,3,4-四羧基二酐(1,1’-bicyclohexane-3,4,3,4-tetracarboxyl dianhydride,H-BPDA)中的至少一种。
所述二胺可以为选自2,2-双[4-(4-氨基苯氧基)-苯基]丙烷(6HMDA)、2,2′-双(三氟甲基)-4,4′-二氨基联苯(2,2′-TFDB)、3,3′-双(三氟甲基)-4,4′-二氨基联苯(3,3′-TFDB)、4,4′-双(3-氨基苯氧基)二苯砜(DBSDA)、双(3-氨基苯基)砜(3DDS)、双(4-氨基苯基)砜(4DDS)、1,3-双(3-氨基苯氧基)苯(APB-133)、1,4-双(4-氨基苯氧基)苯(APB-134)、2,2′-双[3(3-氨基苯氧基)苯基]六氟丙烷(3-BDAF)、2,2′-双[4(4-氨基苯氧基)苯基]六氟丙烷(4-BDAF)、2,2′-双(3-氨基苯基)六氟丙烷(3,3′-6F)、2,2′-双(4-氨基苯基)六氟丙烷(4,4′-6F)、二氨基二苯醚(ODA)和1-(4-氨基苯基)-1,3,3-三甲基-1H-茚-5-胺(TMDA)中的至少一种芳族二胺。然而,所述二胺的实例不限于此。
将所述二酐和二胺以等摩尔量溶解于溶剂中并互相反应,以得到聚酰胺酸溶液。
虽然对反应条件没有特别的限定,优选反应温度为-20~80℃且反应时间为2~48小时。另外,更优选在惰性气体(氩气、氮气等)气氛下进行所述反应。
所述溶剂可以为选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)、丙酮和二乙酸乙酯中的至少一种有机溶剂。
可以采用公知的方法进行使用聚酰胺酸溶液制备聚酰亚胺薄膜的方法。即,可以通过使聚酰胺酸溶液浇铸在支撑体上以对该浇铸的聚酰胺酸溶液进行亚胺化来得到聚酰亚胺薄膜。
在这种情况下,可以通过热亚胺化、化学亚胺化或热亚胺化与化学亚胺化的组合来进行聚酰胺酸溶液的亚胺化。在化学亚胺化中,将由酸酐例如乙酸酐等代表的脱水剂和由叔胺例如异喹啉、β-甲基吡啶、吡啶等代表的亚胺化催化剂加入聚酰胺酸溶液中。在热亚胺化或热亚胺化与化学亚胺化的组合中,可以根据聚酰胺酸溶液的种类和待制备的聚酰亚胺薄膜的厚度来改变聚酰胺酸溶液的加热条件。
在热亚胺化与化学亚胺化组合的情况下,聚酰亚胺薄膜的制备实例具体描述如下。首先,将脱水剂和亚胺化催化剂加入聚酰胺酸溶液,然后浇铸在支撑体上。然后,将浇铸的聚酰胺酸溶液加热到80~200℃,优选100~180℃以使脱水剂和亚胺化催化剂活化并使聚酰胺酸溶液部分固化和干燥,由此将胶化聚酰胺酸薄膜与支撑体分离。然后,将胶化聚酰胺酸薄膜加热到200~400℃保持5~400秒,得到聚酰亚胺薄膜。
随后,在200~400℃下将所述聚酰亚胺薄膜退火200~2000秒,以使得该聚酰亚胺薄膜具有优异的光学各向同性。
此外,在本发明中,所述制备聚酰亚胺薄膜的方法可以包括以下步骤:将二酐和二胺溶解在第一溶剂中并反应以得到聚酰胺酸溶液;使该聚酰胺酸溶液亚胺化;将亚胺化的溶液引入第二溶剂中,然后过滤该亚胺化的溶液并干燥以得到聚酰亚胺树脂固体;将该聚酰亚胺树脂固体溶解在所述第一溶剂中以形成聚酰亚胺溶液;将所述聚酰亚胺溶液浇铸在支撑体上然后干燥该聚酰亚胺溶液。
只要所述第一溶剂可以溶解聚酰胺酸,则对它就没有特别的限定。可以使用选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)、丙酮和二乙酸乙酯中的至少一种极性溶剂(公知的反应溶剂)作为第一溶剂。此外,例如四氢呋喃(THF)、氯仿等低沸点溶剂,或者例如γ-丁内酯等低吸收性溶剂可以用作第一溶剂。
对所述第一溶剂的量没有特别的限定。然而,为了得到具有适当的分子量和粘度的聚酰胺酸溶液,基于聚酰胺酸溶液的总重量,第一溶剂的量可以为50~95wt%,优选为70~90wt%。
同时,在本发明中,聚酰亚胺薄膜也可以如下由所得的聚酰胺酸溶液制备。即,在对所得的聚酰胺酸溶液进行亚胺化后,将该亚胺化的聚酰胺酸溶液引入第二溶剂中,然后沉淀、过滤并干燥,得到聚酰亚胺树脂固体。然后,将所得的聚酰亚胺树脂固体溶解在第一溶剂中,形成聚酰亚胺溶液,然后通过薄膜形成过程使聚酰亚胺溶液形成聚酰亚胺薄膜。
如上所述,聚酰胺酸溶液的亚胺化可以通过热亚胺化、化学亚胺化或热亚胺化与化学亚胺化的组合来进行。根据采用热亚胺化与化学亚胺化的组合对聚酰胺酸溶液进行亚胺化的具体实例,可以通过向所得的聚酰胺酸溶液中加入脱水剂和亚胺化催化剂然后加热聚酰胺酸溶液至20~180℃保持1~12小时来使聚酰胺酸溶液亚胺化。
所述第一溶剂可以与用于聚酰胺酸的溶液聚合中使用的溶剂相同。可以使用不能溶解用于得到聚酰亚胺树脂固体的聚酰胺酸聚合物的溶剂作为所述第二溶剂。另外,在可以应用利用溶解度差使固体沉淀的原理的溶剂中,可以使用极性比第一溶剂低的溶剂作为第二溶剂。具体地,该第二溶剂可以为选自水、醇、醚和酮中的至少一种。
在这种情况下,虽然对第二溶剂的量没有特殊的限定,但优选第二溶剂的用量为要制备的聚酰胺酸溶液总重量的5~20倍。
在过滤所得到的聚酰亚胺树脂固体后,鉴于残留在第二溶剂和固体化的聚酰亚胺树脂中的第一溶剂的沸点,可以在50~150℃温度下将过滤的聚酰亚胺树脂固体干燥2~24小时。
然后,将溶解了聚酰亚胺树脂固体的聚酰亚胺溶液浇铸在支撑体上,然后以1~10℃/min的加热速率在40~400℃内缓慢加热1分钟~8小时,得到聚酰亚胺薄膜。
然后,将所得到的聚酰亚胺薄膜在200~400℃下退火200~2000秒,以使得该聚酰亚胺薄膜具有优异的光学各向同性。
对所述聚酰亚胺薄膜的厚度没有特殊限定。然而,该聚酰亚胺薄膜的厚度可以为10~250μm,优选为25~150μm。
同时,考虑到在相关领域所要求的宽度和加工效率,所述聚酰亚胺薄膜的长度可以优选为0.3~10m的同时,卷绕的聚酰亚胺薄膜的长度可以为10m以上。
下面,将参考以下实施例更详细地描述本发明。
<实施例>
在使氮气通入装配有搅拌器、氮气注入装置、滴液漏斗、温度控制器及冷却器的1L反应器的同时,将405kg的N,N-二甲基乙酰胺(DMAc)加入到该反应器中,将反应器的温度调节为25℃,将40.05kg(2mol)的ODA溶解在该N,N-二甲基乙酰胺(DMAc)中而得到一溶液,然后将该溶液的温度维持在25℃。随后,将61.2kg(2mol)的H-BPDA加入此溶液,然后搅拌30分钟进行反应。将该反应在25℃下进行12小时,得到固体含量为20wt%且粘度为200泊的聚酰胺酸溶液。
反应后,将所得到的聚酰胺酸溶液施用在不锈钢带上,浇铸成125μm的厚度,然后用热风在150℃下干燥20分钟,得到聚酰亚胺薄膜。将此聚酰亚胺薄膜用热风在200℃下热处理10分钟,并用红外光在300℃下热处理10分钟。
之后,作为退火过程,将聚酰亚胺薄膜用红外光缓慢加热至350℃的最高温度保持8.3分钟,然后缓慢冷却。
在这种情况下,所述聚酰亚胺薄膜在纵向(MD)的张力为10N,这是比较低的。为了得到具有低张力的聚酰亚胺薄膜,不通过导辊而利用悬浮来传输聚酰亚胺薄膜(厚度:100μm)。
Claims (5)
1.一种制备透明聚酰亚胺薄膜的方法,该方法采用卷对卷法,其中,成膜是通过将聚酰胺酸溶液或者聚酰亚胺溶液浇铸在支撑体上,然后干燥并加热而进行的;
其中,对上述步骤中干燥并加热的膜进行的退火是在纵向(MD)的张力为10N或小于10N的条件下,在200~400℃下进行退火200~2000秒。
2.根据权利要求1所述的方法,包括以下成膜步骤:
将二酐和二胺溶解在溶剂中并反应以得到聚酰胺酸溶液;和
将所述聚酰胺酸溶液浇铸在支撑体上然后干燥,并加热至200~400℃保持5~400秒以使该聚酰胺酸溶液亚胺化。
3.根据权利要求1所述的方法,包括以下成膜步骤:
将二酐和二胺溶解在第一溶剂中并反应以得到聚酰胺酸溶液;
使所述聚酰胺酸溶液亚胺化;
将亚胺化的溶液引入第二溶剂中,然后过滤该亚胺化的溶液并干燥以得到聚酰亚胺树脂固体;
将所述聚酰亚胺树脂固体溶解在所述第一溶剂中以形成聚酰亚胺溶液;
将所述聚酰亚胺溶液浇铸在支撑体上然后干燥,并加热该聚酰亚胺溶液。
4.根据权利要求2所述的方法,其中,所述溶剂为选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)和丙酮中的至少一种有机溶剂。
5.根据权利要求3所述的方法,其中,所述第一溶剂为选自间甲酚、N-甲基-2-吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)和丙酮中的至少一种有机溶剂;所述第二溶剂为极性比所述第一溶剂低的溶剂,并且为选自水、醇、醚和酮中的至少一种溶剂。
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KR101714892B1 (ko) | 2014-08-26 | 2017-03-09 | 주식회사 엘지화학 | 표면 코팅된 양극 활물질, 이의 제조방법, 및 이를 포함하는 리튬 이차전지 |
WO2016129926A1 (ko) * | 2015-02-11 | 2016-08-18 | 코오롱인더스트리 주식회사 | 폴리아믹산, 폴리이미드 수지 및 폴리이미드 필름 |
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US10316145B2 (en) * | 2016-05-20 | 2019-06-11 | Sk Innovation Co., Ltd. | Polyamic acid composition, polyamideimide film thereof and method for preparing polyamideimide film |
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CN108455995A (zh) * | 2018-02-09 | 2018-08-28 | 青海大学 | 一种碳化硅纤维增强磷酸铝陶瓷基复合材料及其制备方法 |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101796105A (zh) * | 2007-08-27 | 2010-08-04 | 可隆工业株式会社 | 聚酰亚胺膜 |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS606726A (ja) | 1983-06-25 | 1985-01-14 | Nissan Chem Ind Ltd | 新規ポリイミド樹脂及びその製造法 |
US4603061A (en) | 1984-08-23 | 1986-07-29 | The United States Of America As Represented By The National Aeronautics And Space Administration | Process for preparing highly optically transparent/colorless aromatic polyimide film |
US4595548A (en) | 1984-08-23 | 1986-06-17 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for preparing essentially colorless polyimide film containing phenoxy-linked diamines |
JPS6241024A (ja) * | 1985-08-19 | 1987-02-23 | Kanegafuchi Chem Ind Co Ltd | 加熱収縮性の改良されたポリイミドフイルム |
US4645824A (en) | 1985-11-25 | 1987-02-24 | Hughes Aircraft Company | Method of preparing high molecular weight polyimide, product and use |
US5338826A (en) | 1987-07-15 | 1994-08-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administation | Structures from low dielectric polyimides |
US4895972A (en) | 1988-09-01 | 1990-01-23 | The United States Of American As Represented By The Administrator Of The National Aeronautics And Space Administration | Process for lowering the dielectric constant of polyimides using diamic acid additives |
US5218083A (en) | 1989-10-31 | 1993-06-08 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Polyimides prepared from 3,5-diaminobenzotrifluoride |
US5093453A (en) | 1989-12-12 | 1992-03-03 | Administrator Of The National Aeronautics And Space Administration | Aromatic polyimides containing a dimethylsilane-linked dianhydride |
US5218077A (en) | 1991-08-26 | 1993-06-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diphenylmethane-containing dianhydride and polyimides prepared therefrom |
US5367046A (en) | 1992-04-10 | 1994-11-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Low dielectric polyimide fibers |
JP4053603B2 (ja) * | 1996-12-27 | 2008-02-27 | 丸善石油化学株式会社 | 可溶性ポリイミド樹脂、その製法及びポリイミド樹脂溶液組成物 |
US5986036A (en) | 1997-06-27 | 1999-11-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Substrate material for holographic emulsions utilizing fluorinated polyimide film |
JP3066489B2 (ja) * | 1998-07-27 | 2000-07-17 | 鐘淵化学工業株式会社 | ポリイミドフィルムの製造方法 |
US6232428B1 (en) | 1999-01-19 | 2001-05-15 | I.S.T. Corporation | Essentially colorless, transparent polyimide coatings and films |
US7247367B2 (en) | 2001-02-23 | 2007-07-24 | Kaneka Corporation | Polyimide film and process for producing the same |
JP2003335877A (ja) * | 2002-05-17 | 2003-11-28 | Du Pont Toray Co Ltd | ポリイミドフィルムの製造方法 |
JP4318111B2 (ja) * | 2002-09-30 | 2009-08-19 | 東レ・デュポン株式会社 | ポリイミドフィルムおよびその製造方法 |
KR20060123524A (ko) * | 2004-02-27 | 2006-12-01 | 가부시키가이샤 가네카 | Md 방향으로 분자의 배향이 제어된 합성 수지 필름의제조 방법 |
KR20070020420A (ko) * | 2004-03-15 | 2007-02-21 | 가부시키가이샤 가네카 | 신규 폴리이미드 필름 및 그의 이용 |
KR100952796B1 (ko) * | 2004-09-24 | 2010-04-14 | 가부시키가이샤 가네카 | 신규한 폴리이미드 필름 및 이를 이용하여 얻어지는 접착필름, 플렉시블 금속장 적층판 |
US20060127686A1 (en) * | 2004-12-15 | 2006-06-15 | Meloni Paul A | Thermally conductive polyimide film composites having high thermal conductivity useful in an electronic device |
KR101278342B1 (ko) * | 2005-04-28 | 2013-06-25 | 가부시키가이샤 가네카 | 도금용 재료 및 그의 이용 |
JP2006348259A (ja) * | 2005-05-16 | 2006-12-28 | Toyobo Co Ltd | ポリイミドフィルムおよびその製造方法 |
JP2007010883A (ja) * | 2005-06-29 | 2007-01-18 | Sekisui Chem Co Ltd | 位相差フィルムの製造方法 |
JP4661504B2 (ja) * | 2005-09-29 | 2011-03-30 | 富士フイルム株式会社 | 熱可塑性樹脂フィルム及びその製造方法 |
KR20070058812A (ko) * | 2005-12-05 | 2007-06-11 | 주식회사 코오롱 | 폴리이미드 필름 |
US20080118730A1 (en) * | 2006-11-22 | 2008-05-22 | Ta-Hua Yu | Biaxially oriented film, laminates made therefrom, and method |
JP4967853B2 (ja) * | 2007-06-27 | 2012-07-04 | 宇部興産株式会社 | ポリイミドフィルムの製造方法 |
KR101227317B1 (ko) * | 2007-07-31 | 2013-01-28 | 코오롱인더스트리 주식회사 | 열안정성이 개선된 폴리이미드 필름 |
KR101225826B1 (ko) * | 2007-08-20 | 2013-01-23 | 코오롱인더스트리 주식회사 | 무색투명한 폴리이미드 필름 |
-
2010
- 2010-12-31 KR KR20100140836A patent/KR101509831B1/ko active IP Right Grant
-
2011
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- 2011-05-27 WO PCT/KR2011/003909 patent/WO2012091231A1/ko active Application Filing
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- 2011-05-27 US US13/976,571 patent/US20130292873A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101796105A (zh) * | 2007-08-27 | 2010-08-04 | 可隆工业株式会社 | 聚酰亚胺膜 |
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