CN102753615A - 具有良好的拉伸和落镖性质的光可降解的膜 - Google Patents
具有良好的拉伸和落镖性质的光可降解的膜 Download PDFInfo
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Abstract
由聚合物共混物制备的膜结构,该聚合物共混物制包含乙烯/一氧化碳(ECO)共聚物和烯属,特别是乙烯属聚合物,例如,LDPE,其不仅显示光降解,而且显示理想的拉伸和落镖性质。在一个实施方案中,该膜结构为单层,其中ECO共聚物占至少40重量%,且该结构的剩余部分包含LDPE、LLDPE和HDPE至少之一。
Description
技术领域
本发明涉及光可降解的膜。在一方面本发明涉及光可降解的膜,其包含具有从乙烯和一氧化碳(ECO共聚物)衍生的单元的共聚物,在另一方面,本发明涉及包含ECO共聚物的工业、消费品(consumer)和食品包装膜。
背景技术
乙烯/一氧化碳共聚物自从至少20世纪四十年代就已知晓,而它们对光降解的敏感性自从至少20世纪六十年代就已知晓。ECO共聚物在制备工业和消费品包装膜中的用途自从至少20世纪七十年代就已报告,例如,USP 3,676,401,3,929,727和4,714,741和GB 1 448 062。然而,尽管它们具有光降解的环境友好的性质,这些共聚物在工业和消费品包装应用还没有达到预期的认可,因为它们不太理想的机械性质,特别是抗拉性和抗穿刺性。
发明内容
在一个实施方案中本发明为膜结构,其包含乙烯/一氧化碳(ECO)共聚物和非ECO共聚物的烯属、特别是乙烯属聚合物。在一个实施方案中该ECO共聚物占膜结构的至少40,优选至少60至85重量百分比(wt%),剩余的结构包括至少一种非ECO共聚物的烯属、优选乙烯属聚合物。优选的烯烃聚合物包括,但不限于,低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE)和高密度聚乙烯(HDPE)。该膜结构可为单层膜,其中该单层包含ECO共聚物和其它烯烃聚合物两者,或为多层膜,其中(A)所述层中至少之一包含ECO共聚物,和(B)其它层中至少之一(1)包含非ECO共聚物的烯烃聚合物,和(2)不含ECO共聚物。在一个实施方案中,本发明的膜结构为收缩膜,层压膜,衬膜,购物袋,农业膜,食品包装膜状成形充填密封和盒中袋结构,和重型集装袋(HDSS)之一。
附图说明
图1为报告多个本发明的膜和对比膜在加速QUV测试器上暴露于UV光300小时后的百分比伸长的线图。
图2为报告图1中的相同信息的图,所不同的是采用条状图。
具体实施方式
定义
除非另有所述,从上下文暗示,或本领域常规使用的,所有分数和百分比基于重量,所有测试方法为本申请申请日之前的现有技术。出于美国专利实践目的,任何引用的专利、专利申请或出版物的内容以其整体引入作为参考(或其等同的US版本在此引入作为参考),尤其关于以下公开内容:合成技术,产物和工艺设计,聚合物,催化剂,定义(达到不与本申请具体提供的任何定义不一致的程度),和本领域一般知识。
该申请中的数值范围为近似值,因此可包括超过该范围的数值,否则会另外指出。数值范围包括从下限值至上限值的所有值(包括端点),以一个单位为增量,条件是在任何下限值和任何较高值之间有至少两个单元的分离。作为实例,如果组成、物理或其它性质,例如,分子量,重量百分比等,为100至1,000,则预期所有单独的值,如100,101,102,等,和子范围,如100至144,155至170,197至200等,被清楚列举。对于包含小于1的值或包含大于1的分数(例如,1.1,1.5,等)的范围,认为一个单位按需要是0.0001,0.001,0.01或0.1。对于包含小于10(例如,1至5)的单一数字的范围,认为一个单位通常是0.1。这些值仅为具体预期的实例,认为在列举的最低值和最高值之间的数值的所有可能组合在本申请中明确表述。数值范围在本文中尤其对以下提供:衍生自ECO共聚物中一氧化碳的单元的量,膜结构中ECO共聚物的量,和本发明膜结构的各种拉伸性能和穿刺性能。
“组合物”和类似术语是指两种或更多种组分的混合物或共混物。
“聚合物共混物”和类似术语是指两种或更多种聚合物的共混物。该共混物可为或可不为可混合的。该共混物可为或可不为相分离的。该共混物可包含或可不包含一种或多种区域构型,如透射电子光谱学,光散射,X-射线散射,和本领域已知的任何其它方法测定的。
"聚合物"和类似术语是指通过将相同或不同类型的单体反应(即,聚合)制备的大分子化合物。"聚合物"包括均聚物和互聚物。
"互聚物"是指通过聚合至少两种不同单体制备的聚合物。该通用术语包括共聚物,通常用于指由两种不同单体制备的聚合物,和由多于两种不同单体,例如,三聚物、四聚物等制备的聚合物。
“烯烃聚合物”,“基于烯烃的聚合物”和类似术语是指包含50重量%或更多的聚合的烯烃单体(基于聚合物的总重量)的聚合物。该烯烃单体可包括两个或更多个不同的烯烃单体。
“乙烯聚合物,”“基于乙烯的聚合物”和类似术语是指包含50重量%或更多的聚合的乙烯单体(基于聚合物的总重量)的聚合物。
ECO共聚物
本发明实践中使用的ECO共聚物具有的熔体指数(I2,ASTM D1238(190°C/2.16kg))典型为0.1至12,更典型为0.25至6,还更典型为0.25至1.5克/10分钟(g/10min);具有的密度(ASTM D792)典型为0.91至0.95,更典型为0.92至0.94,还更典型为0.922至0.935克/立方厘米(g/cc);具有的一氧化碳含量典型为共聚物的0.1至18,更典型为0.5至10,还更典型为1至3重量%,如红外光谱学测定。一种可用于本发明实践的ECO共聚物可购自The Dow Chemical Company。其为LDPE共聚物,其一氧化碳含量为1wt%,熔体指数(MI或I2)为0.52g/10分钟,且密度为0.93g/cc。ECO共聚物的一氧化碳含量可通过任何常规技术测量,例如,傅里叶变换红外光谱学。
烯烃聚合物
尽管可用于本发明实践中的烯烃聚合物包括基于多种烯烃的聚合物,例如,乙烯,丙烯,丁烯等,用于本发明的优选烯烃聚合物为乙烯属聚合物。这些乙烯属聚合物包括均聚物和互聚物,无规共聚物和嵌段共聚物,和官能化的(例如,乙烯乙酸乙烯酯,乙烯乙基丙烯酸酯,等)和非官能化的聚合物。该乙烯属互聚物包括弹性体、挠性聚合物和塑性体。乙烯聚合物包含至少50,优选至少60且更优选至少80wt%的衍生自乙烯的单元。乙烯属互聚物的其它单元通常衍生自一种或多种α-烯烃。出于本发明目的,ECO共聚物包括在烯烃聚合物的定义中。
该α-烯烃为优选C3-20直链、支链的或环状α-烯烃。C3-20α-烯烃的实例包括丙烯,1-丁烯,4-甲基-1-戊烯,1-己烯,1-辛烯,1-癸烯,1-十二烯,1-十四烯,1-十六烯,和1-十八烯。该α-烯烃也可包含环状结构如环己烷或环戊烷,导致α-烯烃如3-环己基-1-丙烯(烯丙基环己烷)和乙烯基环己烷。尽管并非该术语的经典含义中的α-烯烃,出于本发明目的,某些环状烯烃,如降冰片烯和相关烯烃,特别是5-亚乙基-2-降冰片烯,为α-烯烃且可用于代替上述α-烯烃的一些或全部。类似的,对于本发明目的而言,苯乙烯和其相关烯烃(例如,α-甲基苯乙烯等)为α-烯烃。示例性乙烯属互聚物包括乙烯/丙烯,乙烯/丁烯,乙烯/1-己烯,乙烯/1-辛烯,乙烯/苯乙烯等的共聚物。示例性乙烯属三聚物包括乙烯/丙烯/1-辛烯,乙烯/丙烯/丁烯,乙烯/丁烯/1-辛烯,乙烯/丙烯/二烯单体(EPDM)和乙烯/丁烯/苯乙烯。
用于本发明实践的乙烯属聚合物的实例包括高密度聚乙烯(HDPE);中密度聚乙烯(MDPE);低密度聚乙烯(LDPE);非常低密度聚乙烯(VLDPE);均匀支链的,线性乙烯/α-烯烃共聚物(例如Mitsui Petrochemicals CompanyLimited的和DEX-Plastomers的);均匀支链的,基本上线性的乙烯/α-烯烃聚合物(例如,可获自The Dow Chemical Company的聚烯烃塑性体和聚烯烃弹性体);和乙烯嵌段共聚物(也可获自The Dow Chemical Company)。基本上线性的乙烯共聚物更充分描述于USP 5,272,236,5,278,272和5,986,028,且该乙烯嵌段共聚物更充分描述于USP7,579,408,7,355,0897,524,911,7,514,517,7,582,716和7,504,347。
用于本发明实践的特别感兴趣的烯属互聚物为LDPE,线性低密度聚乙烯(LLDPE)和HDPE。这些乙烯属共聚物可商购自许多不同来源,包括TheDow Chemical Company的商标名为DOWLEXTM,ATTANETM和FLEXOMERTM的产品;Equistar/LyondellBasell的商标名为PETROTHENE的产品;Nova Chemical Company的商标名为NOVAPOL和SCLAIR的产品;和ExxonMobil Chemical Company的商标名为EXCEED,EXACT和ENABLE的产品。
膜结构
本发明有用的膜结构或制品包括流延薄膜,吹塑薄膜,压延薄膜和挤压涂布薄膜(包括,但不限于,多层膜,温室膜,收缩膜(包括透明收缩膜),层压膜,双轴取向薄膜,挤压涂层,衬里,透明衬里,外包装膜和农用薄膜)。单层和多层膜可根据USP 5,685,128描述的膜结构和制备方法制备。
如果膜结构为单层,则该ECO共聚物和烯属互聚物,例如,LDPE,彼此以及和任选的添加剂(包括一种或多种其它聚合物),若有的话,以任何方便的方式共混,例如,干共混单独的成分,且随后或者在用于制备膜的挤出机中直接熔融混合,或在单独的挤出机中预熔融混合,且使用任何膜制备方法,例如,吹塑膜,流延膜等制备为膜。该ECO共聚物占ECO/烯烃聚合物共混物的至少40,50,60,70,80或90wt%,且烯烃共聚物占该共混物的至少1,10,20,30或40wt%。特别感兴趣的为单层膜结构,或多层膜结构,在该多层膜结构中至少一个膜层由包含以下物质的共混物的组合物制备:60-85wt%ECO共聚物(具有的CO含量为0.5-2wt%)和40-15wt%的选自LDPE,LLDPE和HDPE的至少一种。在一个实施方案中该膜结构由包含40至90wt%,优选60至85wt%的ECO共聚物和60至10wt%,优选40至15wt%的LDPE,LLDPE或HDPE,优选LLDPE的聚合物共混物制备。
如果膜结构为多层,则该ECO共聚物可占该结构的一层或多层的全部(100wt%),但通常并非所有层,或其可存在于该结构的一层或多层,包括在每一层中,作为ECO共聚物/烯烃聚合物共混物的一部分。在其中一层或多层没有ECO共聚物的膜结构中,则这些层通常在该结构中安置使得与不包含ECO共聚物的至少一层具有界面接触。
本发明的膜具有许多应用,包括外包装膜如织物外包装,捆绑瓶装水外包装;透明膜如糖果袋,面包袋,开窗信封膜;食品和专用包装膜,如产品袋,肉制品包装,乳酪包装,等;小袋如牛奶袋,盒中袋如酒和其它垂直式样填充和密封技术,如Dow,DuPont和Exxon所教导的。收缩膜特别在本发明的范围内,且这些可使用多种技术制备,如双气泡膜,拉幅机技术,双轴取向技术。本发明的膜也可为弹性的。
有用的膜结构也适当地从包含以下物质的聚合物共混物制备:ECO共聚物,LDPE、LLDPE和HDPE至少之一的乙烯属共聚物,和至少一种非ECO共聚物和乙烯属共聚物的其它天然或合成聚合物。优选的其它聚合物包括,但不限于,热塑塑料,如苯乙烯-丁二烯嵌段共聚物,聚苯乙烯(包括高抗冲聚苯乙烯),乙烯乙烯基醇共聚物,乙烯丙烯酸共聚物,聚酰胺,聚醚,聚氨酯,聚酯,纤维素等。如果存在的话,这些其它聚合物通常占聚合物共混物少于50wt%,更典型的少于40wt%,甚至还典型的少于20wt%。
该ECO共聚物和烯烃聚合物共混物,单独或与一种或多种上述的其它聚合物组合,可按需要与各种添加剂共混,该添加剂如抗氧化剂,紫外线吸收剂,防雾剂,抗静电剂,成核剂,润滑剂,阻燃剂,防粘连剂,着色剂,无机或有机填料等。如果使用的话,这些添加剂以已知的方式和已知的量使用,包括,但不限于,以母料的一部分添加且量通常为0.01至10或更多wt%,基于膜结构的总重量(但填充剂可以更大的量使用)。
如上所述,本发明的膜结构可通过常规制造技术制备,例如简单起泡挤压,双轴取向方法(如拉幅机或双起泡过程),简单流延/板挤压,共挤压,层压等。常规简单起泡挤压方法(也称热吹塑膜方法)描述于,例如,The Encyclopedia of Chemical Technology,Kirk-Othmer,Third Edition,John Wiley& Sons,New York,1981,Vol 16,pp.416-417和Vol.18,pp.191-192。双轴取向膜制备方法如描述于USP 3,456,044的"双起泡"方法中的方法,和描述于USP 4,352,849,4,820,557,4,837,084,4,865,902,4,927,708,4.952,451,4,963,419和5,059,481中的方法也可用于制备本发明的膜结构。双轴取向的膜结构也可通过拉幅机技术,如有用取向的聚丙烯的技术制备。
多层结构的厚度通常为1至4mils(总厚度)。多层膜结构通常包含2至7层,但对于层总数的唯一限制为经济和实用性的影响。对于单层膜,厚度通常为0.4至4mils,优选0.8至2.5mils。
本发明的膜结构可制备为包装结构如成形充填密封结构和盒中袋结构。关于成形充填密封和盒中袋结构,一个这种操作描述于Packaging Foods WithPlastics by Wilmer A.Jenkins和James P.Harrington(1991),pp.78-83。包装也可从多层包装卷筒材料通过垂直或水平成形充填形成(参见包装和热成形充填密封包装,这描述于"Packaging Machinery Operations:No.8,form-fill-sealing,A Self-Instructional Course"by C.G.Davis,PackagingMachinery Manufacturers Institute(1982年四月);The Wiley Encyclopedia ofPackaging Technology by M.Bakker(Editor),John Wiley & Sons(1986),pp.334,364-369;和Packaging:An Introduction by S.Sacharow and A.L.Brody,Harcourt Brace Javanovich Publications,Inc.(1987),pp.322-326)。用垂直成形充填密封机制备小袋的方法通常描述于USP 4,503,102和4,521,437。包含ECO共聚物的含一层或多层的膜结构良好适用于包装适于饮用的水,酒,调味品,和类似食品。
挤压涂覆为制备多层包装材料的另一技术。类似于流延膜,挤压涂覆为平模技术。膜可以单层或复合膜的形式挤压涂布或层压至基底上。该膜结构也可成形为盖子托盘(lid stock)用于注塑的、吹塑的或热成形的盘。
在本发明一个实施方案中,该膜结构为收缩膜。一旦暴露于热,收缩膜会收缩,或如果受限制的话,在膜内产生收缩张力。当包装的产品通过热空气或热水收缩通道时该热反应通常激活。通常,该方法围绕产品引起膜收缩以产生与产品的轮廓一致的紧的、透明的包装,同时防止产品灰尘和污染。
有两种主要类型的热收缩膜--热吹收缩膜和定向收缩膜。热吹收缩膜通过热吹简单气泡膜方法制备,相反,定向收缩膜通过精细的双轴取向方法制备,该方法称为双气泡(double bubble)、带气泡(tape bubble)、禁锢气泡(trappedbubble)或拉幅机拉幅(tenter framing)。无定形和半结晶聚合物都可使用精细的双轴取向方法制备为定向收缩膜。对于无定形聚合物,该取向在稍高于聚合物的玻璃转化温度的温度进行。对于半结晶聚合物,该取向在低于聚合物的峰值熔点的温度进行。
收缩膜及其制备和使用更详细描述于USP 6,306,969,5,972,444,5,852,152,和5,707,751和EP 1 532 203和1 529 633。
本发明通过以下实施例更详细描述。除非另有所述,所有分数和百分比基于重量。
具体实施方案
物理性质
测试方法
用于密度测量的样品根据ASTM D1928制备。测量使用ASTM D792方法B在样品压制1小时内进行。
熔体指数,或I2,根据ASTM D1238测量,条件190°C/2.16kg.
落镖冲击强度(落镖A):ASTM D1709.
45°光泽:ASTM D2457.
总(全部)雾度、表面雾度和内雾度:将用于测定内雾度和总雾度的样品取样并根据ASTM D1003制备。内雾度使用矿物油在膜两侧通过折射指数匹配获得。Hazegard Plus(BYK-Gardner USA;Columbia,MD)用于测试。表面雾度由总雾度和内雾度的差确定,如以下方程所示。表面雾度倾向于与膜的表面粗糙度相关,其中表面雾度随着表面粗糙度增加而增加。
雾度=内雾度+表面雾度 (方程)
刺穿在Instron模型4201上使用Sintech Testworks软件Version 3.10测量。试样尺寸为6”x6”且测量4次以测定平均刺穿值。该膜在制备后处理40小时且在ASTM控制的实验室中保持至少24小时。将100lb测力计与12.56”平方的圆试样保持器一起使用。刺穿探针为1/2”直径抛光的不锈钢球,具有7.5”最大移动长度。没有计量长度;该探针尽可能接近,但不接触试样。使用的十字头速度为10”/分钟。厚度在试样的中间测量。膜的厚度、十字头移动的距离、和最大负荷用于通过软件测定穿刺。刺穿探针使用“Kim-wipe”在各试样后清洗。
2%正割模量-MD(机器方向)和CD(横向):ASTM D882。
MD和CD Elmendorf撕裂强度:ASTM D1922.
MD和CD抗拉强度:ASTM D882.
MD和CD极限伸长:ASTM D822.
MD和CD屈服应变:ASTM D822.
MD和CD屈服强度:ASTM D822.
MD和CD的收缩张力根据以下描述的方法测量:Y.Jin,T.Hermel-Davidock,T.Karjala,M.Demirors,J.Wang,E.Leyva,and D.Allen,“shrink Force Measurement of Low Shrink Force Films”,SPE ANTECProceedings,p.1264(2008)。
方法材料和条件
给出四个实例,两个为本发明,两个为对比例。相同的吹塑膜生产线用于制备本发明的膜和对比膜。实施例1的膜包含85wt%的乙烯和一氧化碳的乙烯属共聚物(LDPE)(MI或I2为0.52g/10分钟,密度为0.930g/cc且CO含量为1wt%)和15wt%ELITE 5111G(I2为0.85g/10分钟,密度为0.9255g/cc且没有任何CO含量),都可获自The Dow Chemical Company。对比例1(CE-1)的膜包含85wt%LDPE 535E(MI为0.60g/10分钟,密度为0.928g/cc且没有任何CO含量,也可获自The Dow Chemical Company)和15wt%ELITE5111G。实施例2的膜包含60wt%的实施例1的含CO的LDPE和40wt%ELITE 5111G。对比例2(CE-2)的膜包含60wt%LDPE 535E和40wt%ELITE 5111G。熔体指数根据ASTM D1238测量(190°C/2.16kg),且密度根据ASTM D792测量。
实施例1和2以及CE-1和2的吹塑膜以6”模制备为具有LLDPE型螺旋。不使用内部鼓泡冷却。各聚合物的粒料以它们的适当比例物理共混,然后将粒料的物理共混物通过粒料漏斗加料至挤出机。用于制备吹塑膜的总的吹塑膜参数在表1中给出。给出的温度开始接近该粒料漏斗并跟随聚合物移动至模头和通过模头(熔融温度)而变化。各膜的吹塑比(BUR)示于表1,且各膜制备为2.5mil的厚度。膜性质示于表2。
表1
吹塑膜工艺条件
表2
膜性质
结果
表2报告的结果显示,相比于没有ECO共聚物的膜,在包含ECO共聚物的膜的许多机械性质方面具有显著的改善而没有明显削弱其它机械性质。尽管包含ECO共聚物的膜比除了没有ECO共聚物之外在所有方面都类似的膜(这是已知的)光降解更快,但是这些包含ECO共聚物的膜也显示增强的落镖A,其对于收缩和韧性是重要的。这些膜也显示增强的光泽(Ex.2vs.CE-2)和屈服应变MD(Ex.2vs.CE-2),其对于目标外观或例如开放的边缘或区域(其为通过它来携带收缩包装的水瓶等的“把手”)的外观是重要的,和对于收缩重要的MD收缩张力。此外,本发明的膜显示对更高密度较低的模量(Ex.1vs.CE-1的2%正割模量CD),提高的CD和MD Elmendorf撕裂,和更高的极限CD和MD拉伸和伸长。
光降解
使用测量表2中报告的膜物理性质的相同的材料和膜制备方法,根据ASTM D5208-01将5个膜(各2.5mil厚)在Q-lab,模型QUV/se的QUV测试器上经受300小时的UV光。将样品切成3英寸×4.5英寸片,因为窗口为2.5英寸×3.75英寸。两个样品按持续时间从各窗口切割。对于总共6个平行测定,每样品每期间使用三个窗口。对于测试器中的每24小时,在50°C有20小时光和在40°C有4小时暗。QUV测试器中的300小时相当于250光亮小时(其为环境保护局的降解指定)。
各样品根据ASTM D3826测量百分比伸长。认为QUV测试器中300小时后具有少于5%伸长的样品是降解的。
QUV和百分比伸长检测的结果在图1和2中给出。在QUV测试器中只有包含至少60wt%含CO的LDPE的那些样品在300小时后降解。
尽管本发明已通过上述具体实施方案用一些具体细节进行了描述,但该细节主要是为了解释的目的。本领域技术人员可进行许多改变和修饰而不偏离权利要求所述的本发明的实质和范围。
Claims (10)
1.由聚合物共混物制备的膜结构,该共混物包含(i)40至90wt%的乙烯/一氧化碳(ECO)共聚物,和(ii)60至10wt%的至少一种选自LDPE、LLDPE和HDPE的乙烯共聚物。
2.权利要求1所述的膜结构,其中该ECO共聚物包含0.1至18wt%的一氧化碳。
3.权利要求2所述的膜结构,其中该聚合物共混物包含(i)60至85wt%的ECO共聚物,和(ii)40至15wt%的至少一种选自LDPE,LLDPE和HDPE的乙烯属共聚物。
4.权利要求3所述的膜结构,其中该乙烯属共聚物为LLDPE。
5.权利要求2所述的膜结构,其作为单层膜。
6.权利要求2所述的膜结构,其作为多层膜,其中所述层中至少之一包括该ECO共聚物。
7.权利要求6所述的膜结构,其中至少一个膜层为100wt%ECO共聚物。
8.权利要求2所述的膜结构,其为收缩膜,层压膜,衬膜,购物袋,农业膜,食品包装膜或重型集装袋的形式。
9.权利要求1-8任一项所述的膜结构,其具有的MD收缩张力至少为15cN。
10.权利要求1-8任一项所述的膜结构,其具有的通过ASTM D1709测定的落镖冲击强度(落镖A)为至少150g。
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US28574109P | 2009-12-11 | 2009-12-11 | |
US61/285,741 | 2009-12-11 | ||
PCT/US2010/059167 WO2011071843A1 (en) | 2009-12-11 | 2010-12-07 | Photodegradable films with good tensile and dart properties |
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CN102753615A true CN102753615A (zh) | 2012-10-24 |
CN102753615B CN102753615B (zh) | 2014-05-28 |
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US (1) | US8859671B2 (zh) |
EP (1) | EP2510049B1 (zh) |
JP (1) | JP5723385B2 (zh) |
KR (1) | KR20120103697A (zh) |
CN (1) | CN102753615B (zh) |
BR (1) | BR112012014024B1 (zh) |
MX (1) | MX2012006658A (zh) |
MY (1) | MY161385A (zh) |
RU (1) | RU2012129179A (zh) |
WO (1) | WO2011071843A1 (zh) |
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CN103009761A (zh) * | 2012-12-25 | 2013-04-03 | 海南赛诺实业有限公司 | 一种高收缩率聚烯烃热收缩薄膜及其制造方法 |
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Also Published As
Publication number | Publication date |
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EP2510049B1 (en) | 2017-01-25 |
KR20120103697A (ko) | 2012-09-19 |
EP2510049A1 (en) | 2012-10-17 |
RU2012129179A (ru) | 2014-01-20 |
CN102753615B (zh) | 2014-05-28 |
US20120289645A1 (en) | 2012-11-15 |
JP2013513695A (ja) | 2013-04-22 |
US8859671B2 (en) | 2014-10-14 |
MX2012006658A (es) | 2012-09-12 |
JP5723385B2 (ja) | 2015-05-27 |
MY161385A (en) | 2017-04-14 |
BR112012014024B1 (pt) | 2019-09-03 |
WO2011071843A1 (en) | 2011-06-16 |
BR112012014024A2 (pt) | 2017-03-28 |
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