CN101687356B - 制造聚乙烯-聚丙烯多层吹塑膜的方法 - Google Patents
制造聚乙烯-聚丙烯多层吹塑膜的方法 Download PDFInfo
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Abstract
本发明涉及制造包括至少一个聚乙烯(除高压聚乙烯以外)层和至少一个聚丙烯层的多层膜的方法,其中,通过以低于10秒的冷固时间对所述膜进行处理来提高所述聚乙烯和聚丙烯之间的粘着力,且无需使用任何粘结层。
Description
本发明涉及制造含有至少一个聚乙烯层和至少一个聚丙烯层的多层膜的方法。
聚乙烯因其透明性、柔韧性、热密封性、抗冲击性、抗撕裂性和感官性能而被广泛用于膜应用。通常,聚乙烯与赋予膜刚性的其它聚烯烃例如聚丙烯一起共挤出、层压或结合。然而,本领域中已知,当无粘结层时,聚乙烯不会粘着到聚丙烯上。典型的粘结层是昂贵的并且需要较复杂的挤出机。
因此,需要在无粘结层时、通过对聚乙烯和聚丙烯进行共挤出来制备具有聚乙烯的总体性能和聚丙烯的良好刚性的膜。
WO97/44178涉及由至少一个茂金属线型低密度聚乙烯层和至少一个冲击级聚丙烯层制成的共挤出吹塑膜,以及由共挤出吹塑膜制成的包装器件。
US5,789,029涉及具有基本上单侧粘着性质的多层热塑性拉伸缠绕膜,其不使用具有高含量的正己烷提取物、不相似的聚合物化学或低分子量增粘剂的聚合物制备。背面或粘着层包括至少一种具有约0.90g/cm3或更小的密度的均相支化乙烯聚合物组合物,且正面或非粘着层包括具有大于0.90g/cm3的密度的丙烯或乙烯聚合物组合物。
本发明的目的是提供通过对聚乙烯和聚丙烯进行共挤出且不使用粘结层而制备膜或片材的方法。
本发明的另一目的是提高聚乙烯和聚丙烯之间的粘着力。
本发明提供制造含有与至少一个聚丙烯层相邻的至少一个聚乙烯层的多层膜的方法,该方法包括如下步骤:
a)将聚丙烯进料到共挤出膜装置的第一挤出机中,
b)将聚乙烯进料到所述共挤出膜装置的第二挤出机中,
c)将所述聚丙烯和聚乙烯通过模口进行共挤出以形成熔融挤出物,
d)将所述熔融挤出物吹塑成膜,
e)将所述膜进行冷却以形成多层膜,
该方法的特征在于,所述挤出物的冷固时间(freezing time)低于10秒且条件是所述聚乙烯不是通过高压聚合方法制造的低密度聚乙烯。
在本发明中,膜定义为极其薄的连续片材:厚度上限为约250微米(Hawley′s Condensed Chemical Dictionary,第12版,R.J.Lewis修订,VanNostrand Reinhold Co.,纽约)。
在本发明中,术语“相邻”是指聚乙烯层与聚丙烯层邻接且不使用任何粘结层。
在本发明中,术语“挤出物的冷固时间”是指挤出物从离开模口时的熔融态变为在霜白线处的结晶固态所用的时间。
在本发明中,通过高压制造的低密度聚乙烯(LDPE)是指通常在压力高于120MPa的高压釜或管式反应器中使用自由基引发剂制造的LDPE。这种低密度聚乙烯的制造是本领域已知的且描述于例如“Encyclopedia of PolymerScience and Engineering”(第二版)的第6卷第404~410页中。
用于本发明的聚丙烯可以是适用于制造膜或片材的任何聚丙烯。其可以是用齐格勒-纳塔催化剂体系制备的丙烯的均聚物或共聚物或三元共聚物、或者这些物质的物理或化学共混物。或者,通过茂金属催化剂体系制造的聚丙烯可以是全同立构或间同立构聚丙烯的均聚物、共聚物(无规或嵌段共聚物)、或三元共聚物,例如在诸如EP-A-881,236、EP-A-965,603、EP-A-1,010,709或WO-00/49209中所公开的那些。
用于本发明的聚乙烯可以是线型低密度聚乙烯、中密度聚乙烯或高密度聚乙烯。
所述聚乙烯可以使用任意已知的催化方法制备,例如使用基于氧化铬的催化剂、齐格勒-纳塔催化剂或茂金属催化剂制备。
基于氧化铬的催化剂、齐格勒-纳塔催化剂和茂金属催化剂是本领域技术人员所公知的。齐格勒-纳塔催化剂包括具有至少一个钛-卤素键的钛化合物和内给电子体(它们均位于合适的载体上(例如位于活性形式的卤化镁上))、有机铝化合物(例如三烷基铝)、和任选的外给体。
茂金属催化剂包括茂金属(其任选地位于合适的载体上)、活化剂(例如铝氧烷)、和任选的第二有机铝化合物(例如三烷基铝)。本文中所用的术语茂金属是指由键合到一个或多个配体上的金属原子构成的任意过渡金属络合物。
铬催化剂是指通过氧化铬在载体(例如二氧化硅或铝载体)上的沉积而得到的催化剂。铬催化剂的实例包括但不限于CrSiO2或CrAl2O3。
当在23℃下、使用ASTM D 1505方法进行测量时,所述聚乙烯的密度可为0.900g/cm3~0.965g/cm3、优选为0.918g/cm3~0.960g/cm3、更优选为0.923g/cm3~0.950g/cm3、且更优选为0.923g/cm3~0.940g/cm3。
本领域已经知道,通过乙烯与适量的选自如下的共聚单体的共聚得到所需的密度:丙烯、1-丁烯、1-己烯、1-辛烯和4-甲基-1-戊烯,优选的共聚单体为1-丁烯、1-己烯、1-辛烯,最优选的共聚单体是1-己烯。
所述聚乙烯的熔融指数可通过注射到反应器中的氢气量来调节。当根据ASTM D 1238在190℃/2.16kg的条件下测量时,所述聚乙烯的熔融指数(MI2)为0.2g/10min~10g/10min、优选为0.3g/10min~2g/10min。
可用于本发明的线型低密度聚乙烯的制造是本领域已知的且描述于例如“Encyclopedia of Polymer Science and Engineering”(第二版)的第6卷第436~444页中。
优选地,用于本发明的聚乙烯是茂金属催化聚乙烯。更优选地,使用具有如下通式的茂金属催化剂制造所述茂金属催化聚乙烯:
R(THI)2MQZ-2
其中,
THI是取代或未取代的四氢茚基,
R是桥接两个四氢茚基的取代或未取代的C1~C4亚烷基、二烷基锗、二烷基硅、二芳基硅、二烷氧基硅烷、二苯氧基硅烷、或者烷基膦或烷基胺基团,
Q是具有1~20个碳原子的烃基、具有1~20个碳原子的烃氧基(hydrocarboxy radical)、或者卤素,其中,所述烃基例如为芳基、烷基、烯基、烷芳基或芳烷基,并且各Q可以彼此相同或者不同,
M是第四族、第五族或第六族过渡金属,且
Z是该过渡金属的化合价。
优选地,THI是未取代的四氢茚基。
优选地,M是第四族过渡金属,更优选地,M是锆。
优选地,Q是具有1~4个碳原子的烷基或者卤素,更优选地,Q是甲基或氯。
优选地,R是取代或未取代的C1~C4亚烷基,更优选为亚乙基或异亚丙基。
优选地,所使用的茂金属催化剂是桥接的双(四氢-茚基)二氯化锆,更优选为亚乙基双(四氢-茚基)二氯化锆。
根据本领域已知的任意方法,将茂金属催化剂用于聚合过程中。
优选地,用于本发明的茂金属催化聚乙烯(mPE)具有单峰分子量分布。分子量分布通过称作分散指数(D)的参数进行限定,所述分散指数是重均分子量(Mw)与数均分子量(Mn)之间的比值。优选地,用于本发明的茂金属催化聚乙烯的分子量分布小于4、优选为2~3、更优选为2.2~2.7。分子量通过凝胶渗透色谱法(GPC)测定。
还可通过长链支化结构来表征mPE。
优选地,用于本发明的mPE树脂具有流变学长链支化指数LCBI,其例如由R.N.Shroff和H.Mavridis在Macromolecules,2001,34,7362-7367中以如下等式进行定义:
其中η0是190℃下的极限零剪切粘度,且[η]是135℃下在三氯苯中的特性粘度。
通过以广义克诺斯(Cross)方程(即η=η0/(1+(γt0)n)对US-A-6114486中所述的流变曲线(复数粘度-频率)进行最小二乘法分析,由最佳拟合计算LCBI,其中,n是材料的幂律指数,其表征该材料的剪切变稀行为;t0是材料的特征松弛时间;η0是零剪切粘度;η和γ分别是所测定的粘度和剪切速率数据。在190℃、氮气下进行动态流变学分析且应变振幅为10%。根据ASTM D 4440报告结果。
优选地,用于本发明的mPE的LCBI至少大于0.14、更优选大于0.50、甚至更优选大于1、最优选大于2。
所述多层膜通过共挤出吹塑方法制造。
在共挤出吹塑方法中,将熔融聚合物通过多通道环状模口挤出以形成管状膜(又称“泡”)。将空气注射到该泡的内部,以使其膨胀至所需直径。通过压料辊,将该泡拉过压平框(collapsing frame),这使所述泡变平为膜。
随着该泡以熔融态从模口表面向上移动,其冷却并达到变为固态的温度。从模口表面到发生固化的位置的距离称作霜白线高度。在该高度处,随着所述膜因聚合物结晶而变得浑浊,所述膜“任选地起霜”。通常,霜白线定义为所述泡具有其最大直径的最低点,因为在该点之上实际上没有进一步的伸展。在共挤出膜方法中,可存在若干霜白线,所述膜的每一层均有一条霜白线。在本发明中,共挤出膜的霜白线是最先冷固的层的霜白线。
挤出物从离开模口时的熔融态变为在霜白线处的结晶固态时所用的时间称作“挤出物的冷固时间”。
当所述泡几乎在刚一高于模口表面时就开始其膨胀的时候,几乎不存在任何“颈”(在本领域中也称为“袋状泡”或称为“LDPE外形(configuration)”),挤出物的冷固时间(Ft)(单位为秒)可由下式定义:
其中,
Fh(m)是霜白线高度,
ln是对数函数,
Vf(m/s)是基料(web)通过压料辊的速度。其也称为膜牵引速度,该速度决定膜的厚度。
Vo(m/s)是熔体输出速度(也称为聚合物离开模口间隙的初始速度)。Vo是熔体密度、模口输出量及模口表面积的函数。Vo根据下式计算:
其中,
Q(kg/s)是输出流速
d(kg/m3)是熔体密度
S(m2)是聚合物离开模口处的模口表面积。
当已经知道膜牵引速度(Vf)、熔体输出速度(Vo)和挤出物的所需冷固时间(Ft)时,则根据上式确定霜白线的高度(Fh)。
泡冷却一般通过在膜离开模口时向该膜吹送大体积的空气来完成。这可以仅在泡的外部进行、或者在泡的内部和外部均进行。为了获得合适的霜白线高度并从而获得挤出物的所需冷固时间,本领域技术人员可通过调节温度和/或空气冲击在所述泡上的速度来调整所述泡的冷却。
由于膜在霜白线处变得浑浊,因而,可目测确定霜白线。
通常手动地使用卷尺进行霜白线高度的测量。
制造膜,使得挤出物的冷固时间低于10秒、优选低于9秒、更优选低于8秒、甚至更优选低于7秒、最优选低于6秒。
特别地,本发明通过如下实现:
1.制造含有与至少一个聚丙烯层相邻的至少一个聚乙烯层的多层片材的方法,该方法包括如下步骤:
a)将聚丙烯进料到共挤出膜装置的第一挤出机中,
b)将聚乙烯进料到所述共挤出膜装置的第二挤出机中,
c)将所述聚丙烯和聚乙烯通过模口进行共挤出以形成熔融挤出物,
d)将所述熔融挤出物吹塑成膜,
e)将所述膜进行冷却以形成多层膜,
该方法的特征在于,所述挤出物的冷固时间低于10秒且条件是所述聚乙烯不是通过高压聚合方法制造的低密度聚乙烯。
2.根据条目1的方法,特征在于,所述挤出物的冷固时间低于9秒。
3.根据条目2的方法,特征在于,所述挤出物的冷固时间低于8秒。
4.根据条目3的方法,特征在于,所述挤出物的冷固时间低于7秒。
5.根据条目4的方法,特征在于,所述挤出物的冷固时间低于6秒。
6.根据前述条目中任一项的方法,特征在于,使用具有如下通式的茂金属催化剂制造所述聚乙烯:
R(THI)2MQZ-2
其中,
THI是取代或未取代的四氢茚基,
R是桥接两个四氢茚基的取代或未取代的C1~C4亚烷基、二烷基锗、二烷基硅、二芳基硅、二烷氧基硅烷、二苯氧基硅烷、或者烷基膦或烷基胺基团,
Q是具有1~20个碳原子的烃基、具有1~20个碳原子的烃氧基、或者卤素,其中,所述烃基选自芳基、烷基、烯基、烷芳基或芳烷基,并且各Q彼此相同或者不同,
M是第四族、第五族或第六族过渡金属,且
Z是该过渡金属的化合价。
7.根据条目6的方法,特征在于M是第IVb族过渡金属。
8.根据条目7的方法,特征在于M是锆。
9.根据条目6的方法,特征在于R是取代或未取代的C1~C4亚烷基。
10.根据条目7的方法,特征在于R是取代或未取代的C1~C4亚烷基.
11.根据条目8的方法,特征在于R是取代或未取代的C1~C4亚烷基。
12.根据条目1~5中任一项的方法,其中所述片材为膜。
13.根据条目6的方法,其中所述片材为膜。
14.根据条目7的方法,其中所述片材为膜。
15.根据条目8的方法,其中所述片材为膜。
16.根据条目9的方法,其中所述片材为膜。
17.根据条目10的方法,其中所述片材为膜。
18.根据条目11的方法,其中所述片材为膜。
当存在多于两个层时,根据一个实施方式,聚丙烯层可为膜或片材的内层且其中外层为聚乙烯。根据另一实施方式,聚丙烯层可为膜或片材的外层且其中内层为聚乙烯。
对于各个实施方式,各膜或片材同时具有高刚性和良好的密封性能。
本发明还提供通过本发明方法制造的吹塑膜或片材。所制造的膜或片材显示出聚乙烯和聚丙烯之间良好的粘着且无需任何粘结层。这是特别令人惊讶的,因为过去认为聚丙烯和聚乙烯难以彼此粘着。
本发明的吹塑膜或片材的特征在于聚乙烯层和聚丙烯层之间的粘着,其与通过相同的共挤出方法在除冷固时间长于或等于11秒以外的相同条件下制造的相同膜的聚乙烯层和聚丙烯层之间的粘着力相比至少高10%、优选至少高20%、更优选至少高50%、甚至更优选至少高100%、最优选至少高200%,其中,在室温下、以200mm/min的速度使用测力计测量所述粘着力。
实施例
1.材料
下列树脂用于本发明方法中:
*茂金属聚乙烯树脂(在下文中称为“R1”),其具有0.923g/cm3的密度和0.9g/10min的MI2。
*茂金属聚乙烯树脂(在下文中称为“R2”),其具有0.927g/cm3的密度和0.9g/10min的MI2。
*茂金属聚乙烯树脂(在下文中称为“R3”),其具有0.934g/cm3的密度和0.9g/10min的MI2。
树脂R1、R2和R3均使用桥接的茂金属亚乙基双(4,5,6,7,四氢-1-茚基)二氯化锆制备。所述催化剂是经活化的和负载的。
*市售的低密度聚乙烯,其由Total Petrochemicals以标号1008FE24出售且在下文中称为“R5”,其具有0.924g/cm3的密度和0.8g/10min的MI2。在高压过程下使用过氧化物制备该树脂。
*市售的聚丙烯,其由Total Petrochemicals以标号PPH3060出售且在下文中称为“R6”。其是由齐格勒-纳塔催化剂制造的丙烯均聚物,具有0.905g/cm3的密度和1.8g/10min的MI2。
*市售的聚丙烯,其由Total Petrochemicals以标号PPR3260出售且在下文中称为“R7”。其是由齐格勒-纳塔催化剂制造的丙烯的无规共聚物,具有0.902g/cm3的密度和1.8g/10min的MI2。
2.膜的制备
制备五个吹塑共挤出的5层A/A/B/C/C膜(在下文中称为F1~F5),且它们的特征在于:
i)由丙烯均聚物(R6)或丙烯的无规共聚物(R7)制成的两个相同的层(层A)。这两个层A的总厚度为50μm。
ii)由前述“1.材料”中所限定的第五种聚乙烯树脂之一构成的一个核心层(层B)。该层B的厚度为10μm。
iii)由聚乙烯树脂R3制成的两个相同的层(层C)。这两个层C的总厚度为70μm。
各膜的总厚度均为130μm。
使用低密度配置(configuration),在吹塑膜生产线装置上对膜进行吹塑,其中,所述低密度配置的特征在于模口直径为50mm、吹胀比为2.5、没有颈且模口间隙为1.4mm。
通过仅在泡的外部的速率为12kg/h的室温空气对泡进行冷却。
3.膜的性质
聚丙烯层与核心聚乙烯层之间的粘着力以分离这些层所必需的力(单位牛顿)来度量。在室温下、以200mm/min的速度使用测力计测量所述粘着力。结果是基于3个样品的平均值。当使用丙烯的无规共聚物作为外层时,结果示于表I中,当使用丙烯的均聚物作为外层时,结果示于表II中。已经分别在图I和II中绘制表I和II的结果。
表I
表II
Claims (16)
1.制造含有与至少一个聚丙烯层相邻的至少一个聚乙烯层的多层片材的方法,该方法包括如下步骤:
a)将聚丙烯进料到共挤出膜装置的第一挤出机中,
b)将聚乙烯进料到所述共挤出膜装置的第二挤出机中,
c)将所述聚丙烯和聚乙烯通过模口进行共挤出以形成熔融挤出物,
d)将所述熔融挤出物吹塑成膜,
e)将所述膜进行冷却以形成多层膜,
该方法的特征在于,所述挤出物的冷固时间低于10秒且条件是所述聚乙烯不是通过高压聚合方法制造的低密度聚乙烯;其中使用具有如下通式的茂金属催化剂制造所述聚乙烯:
R(THI)2MQZ-2
其中,
THI是取代或未取代的四氢茚基,
R是桥接两个四氢茚基的取代或未取代的C1~C4亚烷基、二烷基锗、二烷基硅、二芳基硅、二烷氧基硅烷、二苯氧基硅烷、或者烷基膦或烷基胺基团,
Q是具有1~20个碳原子的烃基、具有1~20个碳原子的烃氧基、或者卤素,其中,所述烃基选自芳基、烷基、烯基、烷芳基或芳烷基,并且各Q彼此相同或者不同,
M是第四族、第五族或第六族过渡金属,且
Z是该过渡金属的化合价。
2.权利要求1的方法,特征在于,所述挤出物的冷固时间低于9秒。
3.权利要求2的方法,特征在于,所述挤出物的冷固时间低于8秒。
4.权利要求3的方法,特征在于,所述挤出物的冷固时间低于7秒。
5.权利要求4的方法,特征在于,所述挤出物的冷固时间低于6秒。
6.权利要求1的方法,特征在于M是第IVb族过渡金属。
7.权利要求6的方法,特征在于M是锆。
8.权利要求1的方法,特征在于R是取代或未取代的C1~C4亚烷基。
9.权利要求6的方法,特征在于R是取代或未取代的C1~C4亚烷基.
10.权利要求7的方法,特征在于R是取代或未取代的C1~C4亚烷基。
11.权利要求1~5中任一项的方法,其中所述片材为膜。
12.权利要求6的方法,其中所述片材为膜。
13.权利要求7的方法,其中所述片材为膜。
14.权利要求8的方法,其中所述片材为膜。
15.权利要求9的方法,其中所述片材为膜。
16.权利要求10的方法,其中所述片材为膜。
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EP07110837.7 | 2007-06-22 | ||
EP20070110837 EP2006070A1 (en) | 2007-06-22 | 2007-06-22 | Process for producing a polyethylene-polypropylene multilayer blown film |
PCT/EP2008/057912 WO2009000783A1 (en) | 2007-06-22 | 2008-06-20 | Process for producing a polyethylene-polypropylene multilayer blown film |
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CN101687356A CN101687356A (zh) | 2010-03-31 |
CN101687356B true CN101687356B (zh) | 2013-01-30 |
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US (1) | US8337743B2 (zh) |
EP (2) | EP2006070A1 (zh) |
JP (1) | JP2010530323A (zh) |
KR (1) | KR101146543B1 (zh) |
CN (1) | CN101687356B (zh) |
WO (1) | WO2009000783A1 (zh) |
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TW201231274A (en) * | 2010-11-18 | 2012-08-01 | Total Petrochemicals Res Feluy | Improved adhesion between polypropylene and polyethylene layers |
CN103407140B (zh) * | 2013-07-26 | 2015-07-01 | 常州大学 | 一种pp/pe/pp三层复合微孔膜的制备方法 |
CN104311979A (zh) * | 2014-09-19 | 2015-01-28 | 金发科技股份有限公司 | 一种乙烯-醋酸乙烯共聚物防伪薄膜及其制备方法 |
CN104312034B (zh) * | 2014-09-19 | 2017-06-09 | 金发科技股份有限公司 | 一种聚氯乙烯防伪薄膜及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1173430A (zh) * | 1996-07-05 | 1998-02-18 | 威司克斯公司 | 用于包装袋内烹调食品的多层塑料复合膜 |
US5840430A (en) * | 1993-12-08 | 1998-11-24 | The Dow Chemical Company | Stretch cling film and fabrication method |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61116521A (ja) * | 1984-11-13 | 1986-06-04 | Mitsubishi Chem Ind Ltd | インフレ−シヨンフイルム成形方法 |
JPH0698680B2 (ja) * | 1985-04-05 | 1994-12-07 | 三菱化成株式会社 | 線状低密度ポリエチレンインフレ−シヨンフイルムの成形方法 |
JPS6392447A (ja) * | 1986-10-07 | 1988-04-22 | 三菱化学株式会社 | 金属とポリオレフインの積層体の製造方法 |
JP2727115B2 (ja) * | 1989-05-08 | 1998-03-11 | 三菱化学株式会社 | 高透明プロピレン重合体フイルム又はシート |
US20050163996A1 (en) * | 1996-01-25 | 2005-07-28 | I-Hwa Lee | Adhesive compositions based on blends of grafted substantially linear polyethylenes and non-grafted conventional polyethylenes |
WO1997044178A1 (en) * | 1996-05-20 | 1997-11-27 | Union Camp Corporation | Coextruded blown film and products made using the same |
US6420501B1 (en) * | 1997-10-22 | 2002-07-16 | Chisso Corporation | Supported metallocene catalyst, process for preparing the same, and process for producing olefin polymers |
JP2001239583A (ja) * | 2000-03-01 | 2001-09-04 | Sumitomo Chem Co Ltd | インフレーションフィルムの製造方法 |
-
2007
- 2007-06-22 EP EP20070110837 patent/EP2006070A1/en not_active Withdrawn
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2008
- 2008-06-20 CN CN2008800212347A patent/CN101687356B/zh not_active Expired - Fee Related
- 2008-06-20 WO PCT/EP2008/057912 patent/WO2009000783A1/en active Application Filing
- 2008-06-20 EP EP08761285A patent/EP2160282A1/en not_active Withdrawn
- 2008-06-20 US US12/665,205 patent/US8337743B2/en not_active Expired - Fee Related
- 2008-06-20 KR KR1020097026588A patent/KR101146543B1/ko not_active IP Right Cessation
- 2008-06-20 JP JP2010512708A patent/JP2010530323A/ja active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5840430A (en) * | 1993-12-08 | 1998-11-24 | The Dow Chemical Company | Stretch cling film and fabrication method |
CN1173430A (zh) * | 1996-07-05 | 1998-02-18 | 威司克斯公司 | 用于包装袋内烹调食品的多层塑料复合膜 |
US5759648A (en) * | 1996-07-05 | 1998-06-02 | Viskase Corporation | Multilayer plastic film, useful for packaging a cook-in foodstuff |
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US20100297459A1 (en) | 2010-11-25 |
US8337743B2 (en) | 2012-12-25 |
EP2160282A1 (en) | 2010-03-10 |
KR20100022990A (ko) | 2010-03-03 |
JP2010530323A (ja) | 2010-09-09 |
WO2009000783A1 (en) | 2008-12-31 |
KR101146543B1 (ko) | 2012-07-11 |
CN101687356A (zh) | 2010-03-31 |
EP2006070A1 (en) | 2008-12-24 |
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