CN1074986C - 用于在袋中包装流动性物料的新型袋 - Google Patents
用于在袋中包装流动性物料的新型袋 Download PDFInfo
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- CN1074986C CN1074986C CN96199357A CN96199357A CN1074986C CN 1074986 C CN1074986 C CN 1074986C CN 96199357 A CN96199357 A CN 96199357A CN 96199357 A CN96199357 A CN 96199357A CN 1074986 C CN1074986 C CN 1074986C
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Abstract
由聚乙烯薄膜结构制得的对环境友好的聚合物薄膜袋(10,20),用于包装流动性材料,例如牛奶。薄膜可以是单层或多层结构(30),例如两层和三层共挤塑薄膜(30),其中含有至少一层(31)超低密度聚乙烯和高压低密度聚乙烯的共混物作为具有高熔体强度的密封层。也公开了使用上述薄膜结构生产用于包装流动性材料的袋(10,20)的方法。
Description
本发明涉及一种用于消费品包装领域由某些薄膜结构制得的的袋,对包装流动性物料例如如牛奶的液体很有用。
美国专利US4,503,102、4,521,437和5,288,531公开了聚乙烯薄膜的制备方法,该薄膜用于制造包装如牛奶的液体的一次性的袋。美国专利US4,503,102公开了一种袋,由乙烯和C4-C10的α-烯烃共聚得到的直链乙烯共聚物和由乙烯和乙酸乙烯酯共聚得到的乙烯-乙酸乙烯酯聚合物的共混物制得。直链聚乙烯共聚物密度为0.916~0.930g/cm3和熔体指数为0.3~2.0g/10min.。乙烯-乙酸乙烯酯聚合物具有乙烯和乙酸乙烯酯的重量比为2.2∶1~24∶1,熔体指数为0.2~10g/10min.。美国专利US4,503,102公开的共混物具有直链低密度聚乙烯和乙烯-乙酸乙烯酯聚合物的重量比为1.2∶1~4∶1。美国专利US4,503,102也公开了具有作为密封层薄膜的上述共混物的层压制品。
美国专利US4,521,437描述了由密封薄膜制得的袋,该薄膜50~100份由乙烯和1-辛烯的直链共聚物(密度为0.916~0.930g/cm3和熔体指数为0.3~2.0g/10min.)和0~50重量份至少一种选自乙烯和C4-C10-α-烯烃的直链共聚物(密度为0.916~0.930g/cm3和熔体指数为0.3~2.0g/10min.)、高压聚乙烯(密度为0.916~0.924g/cm3和熔体指数为1~10g/10min.)和其共混物的聚合物。美国专利US4,521,437公开的密封薄膜的选择基于提供(a)在相同的薄膜厚度下,比由85份直链乙烯/1-丁烯共聚物(密度约0.919g/cm3和熔体指数约0.75g/10min.)和15份高压聚乙烯(密度约0.918g/cm3和熔体指数约8.5g/10min.)的共混物薄膜制得的袋的M-测试值远小的袋,或(b)对于容积大于1.3~5升的袋,M(2)-测试值少于约12%,或(c)对于容积为0.1~1.3升的袋,M(1,3)-测试值少于约5%。在美国专利US4,521,437中M、M(2)和M(1,3)-测试是限定的袋降落测试。袋也可由密封薄膜在其上形成至少内层的复合薄膜制得。
美国专利US5,288,531公开了由薄膜结构制得的袋,该结构具有以下的共混物:(a)10~100wt%的超低密度直链乙烯共聚物的至少一种聚合密封层,该共聚物由乙烯和至少一种C3-C10的α-烯烃共聚制得,密度从约0.89~小于0.915g/cm3和(b)0~90wt%的至少一种聚合物,选自乙烯和C3-C18-α-烯烃的直链共聚物(密度大于0.916g/cm3和熔体指数为0.1~10g/10min.)、高压低密度聚乙烯(密度为0.916~0.930g/cm3和熔体指数为0.1~10g/10min.)或乙烯-乙酸乙烯酯共聚物(其中乙烯和乙酸乙烯酯的重量比为2.2∶1~24∶1,熔体指数为0.2~10g/10min.)。美国专利US5,288,531中的热密封层对于其中描述的两层或三层共挤出多层薄膜结构,提供了提高的热粘着强度和较低的热密封起始温度。
在现有技术中公知的聚乙烯袋有一些不足。与在现有技术中公知的聚乙烯袋有关的问题涉及用于制备袋的薄膜的密封性能和使用性能。具体地说,制成袋的现有技术薄膜一般有“渗漏”的高事故率,即诸如在或接近装有流动性物料的封口处产生小洞的密封缺陷,例如牛奶从袋中漏失。虽然现有技术薄膜的密封和使用性能相对于其它所需性能一般已经满意,但是在工业上在用于装有流动性物料的密封袋生产的薄膜中,仍需要更好的密封和操作性能。更特别的,需要提高的薄膜密封性能诸如热粘着性和提高的熔体强度,以便改进薄膜的加工性能和改进由薄膜制得的袋。
例如,用于生产袋的公知包装设备诸如成型、填充和密封机械的线速度,常常被普通聚乙烯薄膜的密封性能所限制,表面上是由于它们相对低的熔体强度。因此,成型、填充和密封机械能够从普通聚乙烯薄膜生产袋的速度受到限制,同时每一个单位时间生产的袋数也受到限制。为了改进用于袋薄膜的聚合物组合物的密封性能已经做过许多尝试,但没有成功。
需要提供用于袋包装物的聚乙烯薄膜结构,其具有和公知现有技术袋薄膜同样或更好的提高的熔体强度和操作性能。
也需要提供用于袋包装物的薄膜结构,它可以通过成型、填充和密封机械加工成单层或多层薄膜。
还需要提供由上述薄膜结构制得的袋,使得袋具有降低的损坏率。
已经发现当薄膜的熔体强度提高时,在密封区域发生的薄膜变薄的量降低,并因此,成型、填充和密封机械的速度增加,由此每单位时间生产的袋数增加。
本发明的一个方面提供装有流动性物料的袋,该袋由具有至少一种聚合物组合物的密封层的薄膜结构制得,该组合物含有:(A)基于该组合物总重量的10~100wt%的(1)和(2)的混合物:(1)基于100重量份的该混合物,5~95wt%的至少一种超低密度聚乙烯,其为由乙烯和至少一种C3-C18的α-烯烃共聚制得的直链乙烯共聚物,具有:(a)密度从0.89~小于0.916g/cm3(b)熔体指数(I2)小于10g/10min.(c)熔体流动比I10/I2大于5(d)分子量分布,Mw/Mn大于约3(e)由差示扫描量热计测量的峰值熔点大于100℃,和(2)基于100重量份的该混合物,5~95wt%的高压低密度聚乙烯,具有(a)密度从0.916~0.93g/cm3,(b)熔体指数(I2)小于1g/10min.和(c)在190℃用Gottfert Rheotens装置测定的熔体强度大于10cN;和(B)基于该组合物总重量的0~90wt%的至少一种聚合物,选自直链低密度聚乙烯、高压低密度聚乙烯和乙烯-乙酸乙烯酯共聚物。
本发明的一个实施方案是,由含有外层是直链低密度聚乙烯、超低密度聚乙烯、高压低密度聚乙烯、乙烯-乙酸乙烯酯共聚物或其混合物和内密封层是上述聚合物组合物的两层共挤出薄膜制得的袋。
本发明的另一方面是制备上述袋的方法。
本发明的又一实施方案是,由含有外层和芯层是超低密度聚乙烯、直链低密度聚乙烯、高压低密度聚乙烯、乙烯-乙酸乙烯酯共聚物或其混合物和内密封层是上述聚合物组合物的三层共挤出薄膜制得的袋。
已经发现用于本发明的袋的薄膜结构具有提高的熔体强度和相应提高的热密封强度,特别是边缘密封强度。在成型、填充和密封机械上生产本发明的袋的薄膜的使用,导致了机械速度比由于使用市售薄膜的高。
图1表示本发明的包装袋的透视图。
图2表示本发明另一包装袋的透视图。
图3表示本发明袋的薄膜结构的部分、放大截面图。
图4表示本发明袋的薄膜结构的另一部分、放大截面图。
图5表示本发明袋的薄膜结构的又一部分、放大截面图。
图6是装有2升牛奶的袋的边缘密封强度与和高压低密度聚乙烯共混的ATTANETM4203(由Dow化学公司提供的超低密度聚乙烯)的熔体强度的关系曲线的图解。
例如图1和2所示,用于包装流动性物料的本发明的袋,由具有聚合密封层的三层共挤出薄膜结构制得,该聚合密封层由超低密度聚乙烯和高熔体强度的高压低密度聚乙烯构成。共混物也可含有乙烯-乙酸乙烯酯共聚物、直链低密度聚乙烯、均匀支化的基本直链乙烯/α-烯烃共聚物、均匀支化的直链乙烯聚合物、高压低密度聚乙烯或其共混物。
在相关领域也称之为“熔体张力”的“熔体强度”,此处被定义和量化以表示在一些特定速度和其熔点之上,当其经过例如ASTM D1238-E中描述的标准塑度计的拉模时拉伸熔融挤出物所需的应力或力(由装有应变元件的收卷滚筒施加)。此处用厘牛顿(cN)记录的熔体强度值是用GottfertRheotens在190℃时测定的。一般,对于乙烯α-烯烃共聚物和高压乙烯聚合物,熔体强度随着分子量的提高,或随着分子量分布的扩展和/或随着熔体流动比的提高而提高。在190℃用Gottfert Rheotens装置测定时,本发明的高压低密度聚乙烯的熔体强度大于10cN,优选约13~40cN,且最优选15~25cN。另外,在190℃用Gottfert Rheotens装置测定时,本发明的聚合物组合物的熔体强度大于5cN,优选约15~70cN,且最优选15~50cN。
本发明的另一特征是超低密度聚乙烯和直链低密度聚乙烯的峰值熔点大于100℃。峰值熔点用差示扫描量热计(DSC)测定。测试方法的全面描述在Thermal Characterization Of Polymeric Materials,E.A.Turi,(纽约:Academic Press,1981),p.46~59中可以找到。
本发明的聚合物组合物的一个组分是非均相支化的超或非常低密度聚乙烯(ULDPE或VLDPE)。非均相支化的ULDPE在直链聚乙烯领域的专业人员中是公知的。它们通过乙烯和一种或多种任选的α-烯烃共聚单体的连续、间歇或半间歇溶液、淤浆或气相聚合反应制得,使用惯用的齐格勒-纳塔聚合方法和例如Anderson et al.在美国专利US4,076,698中描述的配位金属催化剂。这些惯用的齐格勒型直链聚乙烯不是均相支化的,且它们没有任何的长链分支。由于这些聚合物固有实际上高密度(结晶的)聚合物部分,它们在低密度下也不显示任何实质的非晶形现象。在密度小于0.90g/cm3时,这些材料使用惯用的齐格勒-纳塔催化剂非常难以制备且也非常难以切粒。在密度小于0.90g/cm3时,粒料发粘且趋于结块。
此处使用的术语“非均相的”和“非均相支化的”在通常意义上与具有相对低的短链支化分布指数的直链乙烯共聚物有关。短链支化分布指数被定义为具有在50%的平均总摩尔共聚单体含量范围内的共聚单体含量的聚合物分子的重量百分比。可从溶液中结晶的聚烯烃的短链支化分布指数可以通过公知的温升洗脱分级技术测定,例如Wild,et al.,Journal ofPolymer Science,Poly.Phys.Ed.,Vol.20,p.441(1982),L.D.Cady,“TheRole of Comonomer Type and Distribution in LLDPE ProductPerformance,”SPE Regional Technical Conference,Quaker SquareHilton,Akron,Ohio,十月1-2,pp.107-119(1985),或美国专利US4,798,081中描述的那些。
术语“超低密度聚乙烯”(ULDPE)、“非常低密度聚乙烯”(VLDPE)和“直链非常低密度聚乙烯”(LVLDPE)已经在聚乙烯领域中互相通用,来表示密度小于或等于约0.916g/cm3的直链低密度聚乙烯的聚合物集合。术语“直链低密度聚乙烯”(LLDPE)用来表示那些密度高于0.916g/cm3的直链聚乙烯。这些术语就其本身而言,没有表明聚合物是均相支化的还是非均相支化的,但却表明聚合物的特征在于在术语“直链”的通常意义上其具有直链聚合物骨架。
适合用于本发明的非均相支化的直链共聚物的商品例子包括由Dow化学公司提供的ATTANE ULDPE聚合物和由Union Carbide Corporation提供的FLEOXMER VLDPE聚合物。
ULDPE一般是乙烯和较少量具有3~约18个碳原子、优选4~约10个碳原子且最优选8个碳原子的α-烯烃的直链共聚物。用于本发明聚合物组合物的ULDPE的密度小于或等于0.916g/cm3,更优选0.916~0.89g/cm3,最优选0.90~0.916g/cm3;一般熔体指数(I2)小于10g/10min.,优选0.1~10g/l0min.,最优选0.5~2g/10min.且一般I10/I2为0.1~20,优选5~20,最优选7~20。
适合于本发明ULDPE和LLDPE的α-烯烃由下式表示:
CH2=CHR
其中R是具有1~20个碳原子的烃基。共聚反应方法可以是溶液、淤浆或气相技术或其结合,适合用作共聚单体的α-烯烃包括1-丙烯、1-丁烯、1-异丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯和1-辛烯,以及其它单体类型,例如苯乙烯、卤代或烷基取代的苯乙烯、四氟乙烯、乙烯基苯并环丁烷、1,4-己二烯、1,7-辛二烯,和环烯烃,例如环戊烯、环己烯和环辛烯。优选地,α-烯烃将是1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯,或其混合物。更优选地,α-烯烃将是1-己烯、1-庚烯、1-辛烯,或其混合物,当这样较高级的α-烯烃被用作共聚单体时,用所得到的挤出组合物生产的涂料、型材和薄膜具有特别改进的性能。然而最优选地,α-烯烃将是1-辛烯且聚合方法是连续溶液方法。
乙烯α-烯烃共聚物组合物和高压乙烯聚合物组合物的分子量分布通过凝胶渗透色谱法(GPC),在装有示差折射仪和混合孔隙度的三个柱的Water150高温色谱装置上测定。柱由Polymer Laboratories提供且一般填充成孔隙大小为103、104、105和106,溶剂是1,2,4-三氯代苯,由此制备0.3wt%的样品溶液用于注射。流动速率是1.0ml/min.,单元操作温度是140℃,注射量是100微升。
对于聚合物骨架的分子量测定,通过使用窄分子量分布聚苯乙烯标准(来自Polymer Laboratories)及它们的洗脱容积推定。当量聚乙烯分子量通过使用聚乙烯和聚苯乙烯的适当的Mark-Houwink系数测定(如Williamsand Ward在Journal of Polymer Science,Polymer Letters,Vol.6,p.621,1968所述)以导出下面的等式:
M聚乙烯=a*(M聚苯乙烯)b
在此等式中,a=0.4316且b=l.0。重均分子量Mw用根据下式的通常方式计算:Mw=∑wi×Mi,其中wi和Mi分别是从GPC柱中洗脱出的第i份的重量份数和分子量。
对于ULDPE和LLDPE,Mw/Mn约为2~7,优选大于3且特别约为4。
如此处使用的术语“共聚物”包括二元共聚物,三元共聚物。根据ASTMD-792测试密度。根据ASTMD-1238(条件190/2.16)测试熔体指数(I2)小于10g/10min.和熔体流动比(I10/I2)大于5。根据ASTM D-1238(条件190/10)测试I10。
本发明聚合物组合物的又一组分是下文称之为“直链低密度聚乙烯”(“LLDPE”)的聚乙烯。市售LLDPE的例子是DOWLEXTM2045(DOW化学公司的商标并由其出售)。LLDPE一般是乙烯和少量3~约18个碳原子、优选4~约10个碳原子且最优选8个碳原子的α-烯烃的直链共聚物。用于本发明聚合物组合物的LLDPE的密度大于或等于0.916g/cm3、更优选0.916~0.940g/cm3、最优选0.918~0.926g/cm3;一般具有熔体指数小于10g/10min.、优选从0.1~10g/10min.、最优选从0.5~2g/10min.且一般具有I10/I2比从0.1~20、优选5~20、最优选7~20。
LLDPE可以通过乙烯和一种或多种任选的α-烯烃共聚单体在普通齐格勒Natta催化剂存在下的连续、间歇或半间歇溶液、淤浆或气相聚合反应制备,例如通过Anderson等人的美国专利US4,076,698公开的方法。
用于本发明聚合物组合物和共混物的高压低密度聚乙烯(“LDPE”)是公知的且容易得到。LDPE具有密度为0.916g/cm3~0.930g/cm3,熔体指数(I2)从0.1g~10g/10min.。用于形成和用在本发明的密封层中的超低密度聚乙烯的共混物的LDPE具有熔体强度大于10cN,使用GottfertRheotens装置在190℃时测定。高压低密度聚乙烯的进一步描述可在Modern Plastics Encyclopedia,Mid-October 1992 Issue,Volume 68,Number 11,61~63页中找到。
用于本发明聚合物组合物和共混物的乙烯-乙酸乙烯酯共聚物(“EVA”)具有乙烯和乙酸乙烯酯的重量比从2.2∶1~24∶1,熔体指数从0.2g~10g/10min.。EVA的进一步描述可在Modern Plastics Encyclopedia,Mid-October 1992 Issue,Volume 68,Number 11,66页中找到。
可以相信具有高熔体强度的LDPE在用于本发明的袋的薄膜结构中(1)提供经成型、填充和密封机械快速生产的袋,和(2)提供具有低渗漏的包装袋,特别是当本发明的袋同用直链低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)或其结合体制得的袋相比时。
关于图3~5,本发明的袋的薄膜结构也包括多层或复合薄膜结构30,优选含有作为袋内层的上述聚合物密封层。
本领域熟练人员可以明白,用于本发明的袋的多层薄膜结构可含有薄膜层的各种结合形式,只要密封层形成基本薄膜结构的部分。用于本发明的袋的多层薄膜结构可以是共挤出薄膜、涂敷薄膜或层压薄膜。薄膜结构也包括和防渗薄膜诸如聚酯、尼龙、EVOH、聚偏二氯乙烯(PVDC)例如SARANTM(Dow化学公司的商标)、金属化薄膜和薄金属片一起的密封层。袋的最终用途在很大程度上可以确定其它材料或同密封层薄膜一起使用的材料的选择。此处描述的袋系指至少用在袋内部的密封层。
如图3所示,用于本发明袋的薄膜结构30的一个实施方案包括,超低密度聚乙烯和本发明的高熔体强度LDPE的共混物的密封层31和至少一个聚合物外层32。聚合物外层32优选聚乙烯薄膜层,更优选LLDPE。市售LLDPE的例子是DOWLEXTM(由Dow化学公司出售)。外层32的厚度可以是任意厚度,只要密封层31具有最小厚度约0.1mil(2.5微米)。
如图4所示,用于本发明袋的薄膜结构30的另一实施方案包括夹在两个聚合物密封层31当中的聚合物层32。
如图5所示,用于本发明袋的薄膜结构30的又一实施方案包括在至少一个聚合物外层32和至少一个聚合物密封层31之间的至少一个聚合物芯层33。聚合物层33可以是与外层32相同的聚合物层或优选是不同的聚合物,且更优选LLDPE,例如DOWLEXTM2049(Dow化学公司的商标并由其出售),它比外层32具有更高的密度。芯层33的厚度可以是任意厚度,只要密封层31具有最小厚度约0.1mil(2.5微米)。
用于制造本发明袋的最终薄膜产品的极限薄膜厚度是0.5mil(12.7微米)~10mil(254微米),优选1mil(25.4微米)~5mil(127微米);更优选约2mil(50.8微米)~4mil(100微米)。
对于本领域熟练人员熟知的添加剂,例如防粘剂、滑爽剂、UV稳定剂、颜料和加工助剂,可以加入到制备本发明的袋的聚合物中。
从图3~5所示的本发明的不同实施方案可以看出,用于本发明的袋的薄膜结构具有设计挠性。不同的LLDPE聚合物可以用在外层和芯层,以优化特定的薄膜性质,例如薄膜韧性。因此,对于特定应用例如对于立式成型、填充和密封机械,可以选择薄膜的最佳特性。
用于制备本发明的袋的聚乙烯薄膜结构通过或是吹胀管挤塑方法或是平挤挤塑方法,本领域公知的方法来制备。例如在Modern Plastics,Mid-October 1989 Encyclopedia Issue,Volume 66,Number 11,264~266页中描述了吹胀管挤塑方法。例如在Modern Plastics,Mid-October 1989 Encyclopedia Issue,Volume 66,Number 11,256~257页中描述了平挤挤塑方法。
如图1和2所示,本发明的袋的实施方案是装有“流动性物料”的密封容器。“流动性物料”的意思是在重力下流动的或可以抽吸的物料。术语“流动性物料”不包括气体物料。流动性物料包括液体,例如牛奶、水、水果汁、油;有形流体,化学试剂和用于医疗和诊断的各种液体;乳液,例如冰淇淋混合物,软人造黄油;糊状物,例如肉糊,花生酱;贮藏食品例如果酱,甜饼装填果酱;胶体;生面团;磨碎的肉,例如绞肉;粉末,例如明胶粉末,洗涤剂;粒状固体,例如坚果,糖;和类似材料。本发明的袋特别用于液态食物,例如牛奶。流动性物料也可以包括油质液体,例如烹调油或机油。
在用于本发明的袋的薄膜结构制成后,将薄膜结构切成所需宽度以便用在普通袋成型机械上。如图1和2所示的本发明的袋的实施方案,在本领域公知的所谓的成型、填充和密封机械上实施。关于图1,显示了存在管状部件11的袋10,具有纵向搭接封口12和横向封口13,使得当袋装入流动性物料时,形成“枕形”袋。
关于图2,显示了存在管状部件11的袋20,沿着管状部件21的三边即顶部封口22a和纵向边封口22b和22c,具有周边翼形封口22和封住管状部件21底部的底部基本凹形或“碗形”的部分23,使得当袋装有流动性物料时,纵向观察其截面,基本上形成半圆或“弓形”底部。图2显示的袋是本领域公知的所谓“Enviro-Pak”袋的实例。
根据本发明生产的袋优选是图1显示的袋,在本领域公知的所谓的立式成型、填充和密封(VFFS)机械生产。市售的VFFS机械的例子包括由Hayssen,Thimonnier,Tetra Pak,或Prepac生产的那些。在下面资料中描述了VSSF机械:F.C.Lewis,“Form-Fill-Seal”,PackagingEncyclopedia,第180页,1980。
在VFFS包装方法中,此处描述的塑料薄膜结构的薄片加入到VFFS机械中,其中薄片在管成型部件成型为一个不间断管。管部件成型通过将薄膜的纵向边密封在一起-或是通过使用内外封搭接塑料薄膜并密封薄膜,或是使用内外封翼形封住塑料薄膜。接着,密封条在作为“袋”底部的一端横向封住管,然后填充物料例如牛奶加入到“袋”中。密封条封住袋的上端,或是烧穿塑料薄膜或是切割薄膜,于是从管中分离出成型的完整的袋。在美国专利US4,503,102和US4,521,437中一般描述了用VFFS机械生产袋的方法。
本发明的袋的容积可以改变。一般,袋可以含有从5ml~10l,优选从1l~8l,更优选从1ml~5l的流动性物料。
本发明的袋的薄膜结构具有精确的可控强度。在本发明中描述的薄膜结构用于生产袋,得到了更坚固的袋,并因此更优选地,袋具有较少的与使用相关的渗漏。在本发明中超低密度聚乙烯(ULDPE)和LDPE共混物用于两层或三层共挤出薄膜产品中,将提供可以用于在VFFS中快速生产袋的薄膜结构,且所生产的袋将具有较少的渗漏。
随着当今消费品包装工业提供给消费者对环境更友好的包装的趋势,本发明的聚乙烯袋是好的替代物。用于包装消费品液体例如牛奶的聚乙烯袋的应用,具有的好处超过过去所使用容器:玻璃瓶、纸盒和高密度聚乙烯水罐。以前所用的容器在其生产过程中消耗了大量的天然资源,需要大量的掩埋空间,使用了大量的储存空间并在产品的温控中使用了更多的能量(由于容器的热传递性质)。
本发明的聚乙烯袋,由薄聚乙烯薄膜制得,用于包装流动性物料,提供了许多好处超过过去所使用的容器。聚乙烯袋(1)消耗较少的天然资源,(2)需要较少掩埋空间,(3)可以回收,(4)可以容易地加工,(5)需要较少储存空间,(6)使用较少能量用于储存(包装的热传递性能),(7)可以安全地焚化和(8)可以重复使用,例如空袋可以用于其它应用,诸如冷藏箱袋、面包袋和普通目的的储存袋。
下面表Ⅰ中描述的聚合物树脂用于制备实施例和对比例中示出的吹胀薄膜的试样。
表Ⅰ:树脂性能
树脂名称 | 类型 | 熔体指数dg/min. | 密度g/cm3 | 熔体强度cN |
DOWLEX 2045 | LLDPE | 1.0 | 0.920 | 6.4 |
LDPE135I | LDPE(管) | 0.22 | 0.923 | 19.5 |
XU60021.62 | LDPE(热压罐) | 0.5 | 0.919 | 24.3 |
LDPE609C | LDPE(管) | 0.88 | 0.924 | 12.1 |
LDPE526I | LDPE(管) | 1.0 | 0.922 | 12.1 |
LDPE503I | LDPE(管) | 1.9 | 0.923 | 5 |
ATTANE4203 | ULDPE | 0.8 | 0.905 | 8 |
芥酸酰胺,滑爽剂;SiO2,防粘剂;和加工助剂加入到表Ⅰ中所述树脂的每一个中,使得添加剂的最终浓度如下:1200ppm芥酸酰胺;2500ppmSiO2。
各种高压低密度聚乙烯和超低密度聚乙烯共混物的组合物以及它们的熔体强度列于下面的表Ⅱ中。
表Ⅱ:树脂共混物的熔体强度
(*)%指的是共混物中LDPE的重量百分比。
共混物标记 | 种类(*) | 熔体强度(cN) |
1 | DOWLEX 2045 | 6.4 |
4 | LDPE526I | 12.1 |
5 | LDPE135I | 19.5 |
6 | LDPE609C | 12.1 |
7 | LDPE XU60021.62 | 24.3 |
8 | DOWLEX2045/10%135I | 10.4 |
9 | DOWLEX2045/20%135I | 16.0 |
10 | DOWLEX2045/30%135I | 19.7 |
11 | DOWLEX2045/10%609C | 9.5 |
12 | DOWLEX2045/20%609C | 11.7 |
13 | DOWLEX2045/30%609C | 13.4 |
14 | DOWLEX2045/10%XU60021.62 | 11.5 |
15 | DOWLEX2045/20%XU60021.62 | 24.2 |
16 | DOWLEX2045/30%XU60021.62 | 30.4 |
17 | ATTANE4203/10%135I | 12.0 |
18 | ATTANE4203/20%135I | 15.8 |
19 | ATTANE4203/30%135I | 17.5 |
20 | ATTANE4203/10%526I | 9.5 |
21 | ATTANE4203/20%526I | 10.5 |
22 | ATTANE4203/30%526I | 11.5 |
23 | ATTANE4203/10%XU60021.62 | 16.1 |
24 | ATTANE4203/20%XU60021.62 | 22.8 |
25 | ATTANE4203/30%XU60021.62 | 33.5 |
表Ⅱ中所示的每种共混物的5kg试样,经Leistritz双螺杆挤出机加工,使用Gottfert Rheotoens装置测定共混物的熔体强度。
表Ⅲ:用于物理性能测试的多层(A/B/A)薄膜的树脂共混物
(*)%指的是共混物中LDPE的重量百分比。实施例1-8和对比例A和B
实施例号 | 层A中树脂共混物 | 层B中树脂共混物 | 总厚度(Mils) |
1 | ATTANE4203+20%LDPE135I | DOWLEX2045+80%LDPE135I | 2.43 |
2 | ATTANE4203+20%LDPE503I | DOWLEX2045+20%LDPE503I | 2.50 |
3 | ATTANE4203+20%LDPE526I | DOWLEX2045+20%LDPE526I | 2.51 |
4 | ATTANE4203+20%XU60021.62 | DOWLEX2045+20%XU60021.62 | 2.45 |
对比例A | 100%ATTANE4203 | 100%DOWLEX2045 | 2.53 |
对比例B | 100%DOWLEX2045 | 不适用 | 2.5 |
吹胀薄膜用表Ⅲ所述的树脂共混物使用Egan三层共挤出作业线制备,除了使用Macro单层吹胀薄膜作业线的对比例B外。Egan作业线在标准挤出机条件以吹胀比2.0和熔体温度430°F(239℃)下操作。三层共挤出薄膜由两个相同的表层(A)和芯层(B)以A/B/A构型构成,A∶B∶A的层比等于1∶3∶1。用Macro吹胀薄膜作业线制得的对比例B,在标准挤出机条件以吹胀比2.0和熔体温度420°F(233℃)下操作。按配方制造所有薄膜使得含有相同的滑爽剂、防粘剂和加工助剂含量。在含有LDPE的薄膜中,三层的每一个都如表Ⅲ所示的20wt%的LDPE。
薄膜结构经过物理测试以测定其各种性能,包括:
(1)穿刺,应用方法ASTM D3763;
(2)落镖冲击,应用ASTM D1709,方法A;
(3)Elmendorf撕裂,应用ASTM D1922;
(4)拉伸,应用ASTM D882;
(5)1%和2%正割模量,应用ASTM D882;
(6)热粘着强度,应用下面描述的方法;和
(7)热密封强度,应用下面描述的方法;
应用“DTC热粘着测试方法”测试试样薄膜的热粘着强度,测试在封口已经完全冷却(结晶)前需要分离热密封的力。这模拟了在封口冷却前将物料填充到袋中。
“DTC热粘着测试方法”是根据下面条件使用DTC Hot Tack TesterModel#52D的测试方法:
样品宽度: 25.4mm
密封时间: 0.5秒
密封压力: 0.27N/mm/mm
迟延时间: 0.5秒
剥离速度: 150mm/秒
样品数/温度 5
温度增量: 5℃
温度范围: 75℃-150℃
使用“DTC热密封强度测试方法”测试试样薄膜的热密封强度,这是设计测试在材料冷却到23℃后分离封口所需要的力。在测试前薄膜样品在相对温度50%和温度为23℃下暴露最少24小时。
“DTC热密封强度测试方法”根据下面条件使用了DTC Hot TackTester Model#52D,其中使用了测试仪的热密封部分:
样品宽度: 25.4mm
密封时间: 0.5秒
密封压力: 0.27N/mm/mm
样品数/温度 5
温度增量: 5℃
温度范围: 80℃-150℃
使用Instron Tensile Tester Model#1122根据下面测试条件测定薄膜试样的密封强度:
牵拉方向: 90°密封
十字头速度: 500mm/min.
全规模负载: 5kg
试样数/界限: 1%的FSL
断裂标准: 80%
标距: 2.0英寸
(50.8mm)
试样宽度: 1.0英寸
(25.4mm)
由表Ⅲ中显示的树脂共混物制得的三层(A/B/A)薄膜的物理性能记录于下面的表Ⅳ中,热粘着强度和热密封强度相应地记录于表Ⅴ和表Ⅵ中。
表Ⅳ:三层(A/B/A)共挤塑薄膜的物理性能
种类 | ATTANE4203+20%XU60021.62 | ATTANE4203+20%135I | ATTANE4203+20%503I | ATTANE4203+20%526I | ATTANE4203 | DOWLEX 2045 | ||
标准尺寸 | um | 62.23 | 61.72 | 63.50 | 63.75 | 64.26 | 63.50 | |
Elmendorf撕裂 | g | MDCD | 4531.504 | 6481.734 | 7861.677 | 6741.785 | 1.1601.587 | 9971.424 |
落镖冲击 | g | 352 | 371 | 323 | 335 | 535 | 288 | |
穿刺断裂阻能 | NJ/cm3 | 198.38511.52 | 190.82487.06 | 182.81491.50 | 211.72555.11 | 227.74578.24 | 95.63262.43 | |
拉伸破坏载荷 | N | MDCD | 54.7143.15 | 57.8250.71 | 54.7149.37 | 57.8249.82 | 68.0560.05 | 48.0443.59 |
拉伸极限 | kg/cm2 | MDCD | 366.68281.97 | 367.18329.29 | 338.78315.08 | 360.43313.75 | 441.41379.62 | 322.11295.26 |
伸长 | % | MDCD | 680856 | 671768 | 683775 | 757858 | 725771 | 617682 |
韧度 | J/cm3 | MDCD | 125.2596.63 | 118.63111.52 | 110.86111.02 | 130.05120.04 | 123.60119.54 | 95.5599.19 |
拉伸屈服 | kg/cm2 | MDCD | 104.0486.47 | 98.63102.29 | 96.24102.71 | 93.29102.36 | 99.26104.18 | 110.86133.36 |
1%正割 | kg/cm2 | MDCD | 2394.002530.87 | 2052.762451.99 | 2042.572312.73 | 1866.752208.83 | 1965.312377.90 | 2527.003159.70 |
2%正割 | kg/cm2 | MDCD | 2027.382091.21 | 1715.321949.00 | 1681.511916.87 | 1585.481845.66 | 1640.661964.46 | 2096.772490.38 |
表V:三层(A/B/A)薄膜的热粘着强度(N/25mm)
ATTANE4203+20%XU60021.62 | ATTANE4203+20%135I | ATTANE4203+20%503I | ATTANE4203+20%526I | ATTANE4203 | DOWLEX2045 | |
温度,(℃) | 60021.62 | LDPE135I | LDPE503I | LDPE526I | ||
75 | 0.18 | 0.15 | 0.17 | 0.19 | 0.18 | |
80 | 0.22 | 0.22 | 0.21 | 0.30 | 1.08 | |
85 | 0.81 | 1.51 | 1.49 | 1.25 | 2.18 | |
90 | 1.50 | 2.12 | 1.85 | 1.68 | 2.16 | 0.23 |
95 | 2.79 | 2.83 | 2.11 | 2.08 | 2.55 | 0.17 |
100 | 3.65 | 3.45 | 2.37 | 2.85 | 2.67 | 0.64 |
105 | 3.49 | 3.36 | 2.60 | 2.68 | 2.51 | 1.91 |
110 | 3.37 | 3.31 | 2.66 | 2.52 | 2.31 | 2.47 |
115 | 3.43 | 3.21 | 2.59 | 2.35 | 2.69 | 3.28 |
120 | 2.86 | 2.76 | 2.12 | 1.93 | 2.37 | 2.64 |
125 | 2.49 | 2.25 | 1.92 | 1.74 | 2.23 | 2.51 |
130 | 2.02 | 1.98 | 1.88 | 1.67 | 2.05 | 2.38 |
135 | 1.84 | 1.86 | 1.87 | 1.62 | 1.89 | 2.35 |
140 | 1.70 | 1.79 | 1.68 | 1.54 | 1.70 | 2.27 |
145 | 1.67 | 1.76 | 1.70 | 1.48 | 1.75 | 2.17 |
150 | 1.53 | 1.60 | 1.54 | 1.29 | 1.51 | 1.96 |
表Ⅵ:三层(A/B/A)薄膜的热密封强度(N/25mm)
AFF1880+20%1351(80%LD芯中) | AFF1880+20%1351 | AFF1880+20%XU60021.62 | AFF1880+20%5031 | AFF1880+20%5261 | AFFINITY1880 | ATTANE4203 | EX3033+20%XU60021.62 | EX3033+20%1351 | EX3033+20%5261 | EX3033 | |
℃ | |||||||||||
80 | 1.38 | 0.85 | 1.38 | 0.89 | 0.98 | 1.29 | 1.69 | ||||
85 | 11.56 | 11.92 | 7.65 | 4.31 | 3.83 | 12.28 | 1.73 | 1.60 | 0.36 | 0.22 | 0.89 |
90 | 15.66 | 16.86 | 15.35 | 16.86 | 13.03 | 15.97 | 6.23 | 6.23 | 7.74 | 7.92 | 13.43 |
95 | 19.39 | 19.70 | 17.84 | 19.22 | 15.57 | 17.21 | 15.03 | 17.26 | 18.99 | 16.37 | 17.44 |
100 | 28.60 | 23.62 | 21.53 | 20.46 | 17.97 | 19.53 | 16.68 | 22.15 | 23.13 | 19.70 | 20.55 |
105 | 31.80 | 24.51 | 25.04 | 20.55 | 20.46 | 20.33 | 17.12 | 25.93 | 24.69 | 23.26 | 21.88 |
110 | 34.21 | 25.31 | 25.00 | 20.95 | 20.73 | 20.82 | 18.64 | 25.89 | 26.91 | 23.66 | 22.02 |
115 | 32.47 | 25.22 | 24.73 | 21.80 | 20.37 | 20.99 | 20.06 | 25.80 | 27.40 | 23.71 | 22.42 |
120 | 24.73 | 25.53 | 22.95 | 21.88 | 21.71 | 23.71 | 26.47 | 27.40 | 24.86 | 22.06 | |
125 | 33.80 | 23.62 | 26.55 | 23.26 | 22.68 | 22.20 | 23.44 | 26.73 | 27.93 | 23.71 | 22.15 |
130 | 36.61 | 26.20 | 26.33 | 22.42 | 22.46 | 22.46 | 23.31 | 28.38 | 28.33 | 22.20 | 22.02 |
135 | 37.10 | 24.38 | 26.38 | 23.09 | 23.31 | 23.13 | 23.80 | 27.36 | 27.93 | 24.82 | 22.24 |
140 | 39.01 | 24.29 | 26.29 | 21.97 | 23.84 | 24.78 | 24.11 | 26.47 | 28.42 | 24.15 | 23.57 |
145 | 37.90 | 24.15 | 26.11 | 22.02 | 24.46 | 24.91 | 25.22 | 26.87 | 28.96 | 24.73 | 22.15 |
150 | 39.41 | 24.55 | 25.35 | 21.93 | 23.13 | 24.02 | 25.49 | 29.05 | 29.27 | 25.35 | 22.82 |
本发明通过下面的实施例加以说明,但并不局限于此。实施例9-11和对比例C和D
由表Ⅲ中所述的树脂共混物制得的薄膜纵切成15英寸(38.1cm)的宽度,使用设置于商业化牛奶场的Prepac IS6立式成型、填充和密封机械生产2升牛奶袋。在常规操作条件下装置以每分钟每个装填设备30袋的速度包装装有2升牛奶的袋。对于每个测试的薄膜,收集大约16-20个装有牛奶的袋。它们被检查起始密封完全性。10个袋被排空、清洗和干燥用于进一步测试。
端部密封完全性的起始检查包括三个步骤:
ⅰ)在线渗漏的测定
ⅱ)主观密封强度测试
ⅲ)端部封口的目视检验
在由100%的ATTANE4203和DOWLEX2045制得的袋上观察到在线渗漏。在其它薄膜上没有观察到渗漏。
主观密封强度测试包括从一端挤压袋,直到袋或是屈服或是密封失败。表Ⅶ显示了在由含有20wt%的135I或是XU60021.62的薄膜制得的袋上没有观察到密封失败。
由在密封层中含有ATTANE4203和DOWLEX2045的多层薄膜制得的袋具有如表Ⅷ所示的明显的封口变薄和端部密封拉丝。用20%的LDPE526I制得的袋具有来自密封区域的封口变薄和端部密封拉丝薄膜聚合物长丝。在薄膜的密封层中含有20%的LDPE135I或是LDPEXU60021.62的袋没有发现封口变薄或拉丝。
使用Instron Tensile Tester Model#1122,在与上面热密封强度测定相同的条件下测定2升牛奶袋的端部密封强度。
密封强度显示于表Ⅸ中。当密封层中聚合物共混物的熔体强度提高时,发现密封强度提高。在LDPE熔体指数和密封强度之间显然没有关系。
使用光显微技术低温切割并检查袋的拉丝区域和边缘区域。表Ⅹ总结了结果。
由在密封层中含有20%的LDPE135I或是LDPEXU60021.62制得的袋显示很小的封口变薄和没有端部密封拉丝(来自密封区域的细聚合物长丝),而含有100%ATTANE4203和DOWLEX2045的袋具有明显的封口变薄和拉丝。
好的封口的最差的部分一般是恰在封条前的薄膜。此薄膜的任何变薄导致较低的密封强度,因为这是当封口受压时失败的区域。将树脂共混物的熔体强度(表Ⅱ)与在由商用VFFS装置生产的袋上看到的薄膜变薄的量(表Ⅹ)相比,可以看到,当树脂共混物的熔体强度提高时,薄膜变薄的量降低。在薄膜变薄(表Ⅹ)和树脂共混物中LDPE的熔体指数(表Ⅰ)之间没有关系。
表Ⅶ:市售Dairy Prepac VFFS测定
主观密封强度
实验# | LLDPE | LDPE | %LDPE | #袋测试 | #密封失败 |
对比例C | ATTANE4203 | 0 | 8 | 3 | |
对比例D | DOWLEX2045 | 0 | 7 | 3 | |
9 | ATTANE4203 | 5261 | 20 | 9 | 2 |
10 | ATTANE4203 | 135I | 20 | 0 | |
11 | ATTANE4203 | XU.62 | 20 | 8 | 0 |
表Ⅷ:市售dairy Prepac VFFS测定
端部封口的表观检验
实验# | LLDPE | LDPE | %LDPE | 封口的表观检验 |
对比例C | ATTANE4203 | -- | 0 | 大量拉丝,封口变薄 |
对比例D | DOWLEX2045 | -- | 0 | 大量拉丝,封口变薄 |
9 | ATTANE4203 | 526I | 20 | 一些拉丝,封口变薄 |
1 | ATTANE4203 | 135I | 20 | 无拉丝 |
11 | ATTANE4203 | XU.62 | 20 | 无拉丝 |
表Ⅸ:Prepac VFFS袋端部密封强度
实验 # | LLDPE MI | LDPEMI | %LDPE | 密封强度N/25mm |
对比例C | ATTANE4203 | --- | 0 | 24.89 |
对比例D | DOWLEX2045 | --- | 0 | 23.62 |
9 | ATTANE4203 | 526I | 20 | 24.69 |
10 | ATTANE4203 | 135I | 20 | 25.58 |
11 | ATTANE4203 | XU.62 | 20 | 28.87 |
表Ⅹ:Prepac VFFS显微术分析总结
*从封口处550μm测量**在密封前在薄膜的最薄部分测量横截面。
# | 种类 | 评定 | *薄膜厚度μm | **密封前的薄膜厚度μm | 薄膜厚度减少百分率% |
对比例C | ATTANE4203 | 封口区域急剧变薄和拉丝,许多封口拉丝 | 69.3 | 48.8 | 30 |
对比例D | DOWLEX2045 | 封口区域急剧变薄和拉丝,许多封口拉丝 | 65.5 | 43.1 | 34 |
9 | ATTANE4203+20%LDPE526I | 急剧变薄,许多拉丝 | 69.4 | 49.8 | 28 |
10 | ATTANE4203+20%LDPE135I | 好,没有变薄,没有拉丝 | 76.8 | 70.3 | 8 |
11 | ATTANE4203+20%XU60021.62 | 好,没有变薄,没有拉丝 | 71.5 | 69.8 | 2 |
表Ⅺ显示LDPE135I和ATTANE4203的热粘着数据以及80wt%ATTANE4203和20wt%LDPE135I的共混物的预计和观察的热粘着数值。可以看到,本发明的ATTANE4203和LDPE135I的共混物的观察热粘着强度,明显地比表示清晰协同作用的共混物的预计含量高。 表Ⅺ:热粘着强度-ATTANE
预计值与观测值
ATTANE4203 | LDPE135I | ATTANE4203+20%135I预计的 | ATTANE4203+20%135I观测的 | |
温度℃ | ||||
90 | 2.16 | 0.00 | 1.75 | 2.12 |
95 | 2.55 | 0.18 | 2.09 | 2.83 |
100 | 2.67 | 0.22 | 2.20 | 3.45 |
105 | 2.51 | 0.56 | 2.14 | 3.36 |
110 | 2.31 | 0.81 | 2.02 | 3.31 |
115 | 2.69 | 0.86 | 2.35 | 3.21 |
120 | 2.37 | 0.74 | 2.06 | 2.76 |
125 | 2.23 | 0.69 | 1.94 | 2.25 |
130 | 2.05 | 0.69 | 1.79 | 1.98 |
135 | 1.89 | 0.64 | 1.65 | 1.86 |
140 | 1.70 | 0.64 | 1.50 | 1.79 |
145 | 1.75 | 0.60 | 1.53 | 1.76 |
150 | 1.51 | 0.56 | 1.33 | 1.60 |
由下式计算预计的热粘着强度:
预计的热粘着强度=(0.8×ATTANE4203热粘着强度)+(0.2×LDPE热粘着强度)
Claims (24)
1、装有流动性物料的袋,该袋由具有至少一个聚合物组合物密封层的薄膜结构制得,该组合物包括:
(A)基于该组合物总重量的10~100wt%的(1)和(2)的混合物:(1)基于100重量份的该混合物,5~95wt%的至少一种超低密度聚乙烯,其为由乙烯和至少一种C3-C18的α-烯烃共聚制得的直链乙烯共聚物,且具有:(a)密度从0.89g/cm3~小于0.916g/cm3,(b)熔体指数(I2)小于10g/10min.,(c)熔体流动比I10/I2大于5(d)分子量分布,Mw/Mn大于3(e)由差示扫描量热计测量的峰值熔点大于100℃,和(2)基于100重量份的该混合物,5~95wt%的高压低密度聚乙烯,具有(a)密度从0.916g/cm3~0.93g/cm3,(b)熔体指数(I2)小于1g/10min.和(c)在190℃用Gottfert Rheotens装置测定的熔体强度大于10cN;和
(B)基于该组合物总重量的0~90wt%的至少一种聚合物,选自直链低密度聚乙烯、高压低密度聚乙烯和乙烯-乙酸乙烯酯共聚物。
2、装有流动性物料的袋,该袋由含有下面的多层薄膜结构制得:
(Ⅰ)一聚合物组合物层,含有:
(A)基于该组合物总重量的10~100wt%的(1)和(2)的混合物:(1)基于100重量份的该混合物,5~95wt%的至少一种超低密度聚乙烯,其为由乙烯和至少一种C3-C18的α-烯烃共聚制得的直链乙烯共聚物,且具有:(a)密度从0.89g/cm3~小于0.916g/cm3,(b)熔体指数(I2)小于10g/10min.,(c)熔体流动比I10/I2大于5,(d)分子量分布,Mw/Mn大于3,(e)由差示扫描量热计测量的峰值熔点大于100℃;和(2)基于100重量份的该混合物,5~95wt%的高压低密度聚乙烯,具有密度从0.916~0.93g/cm3,熔体指数(I2)小于1g/10min.和在190℃用Gottfert Rheotens装置测定的熔体强度大于10cN;和
(B)基于该组合物总重量的0~90wt%的至少一种聚合物,选自直链低密度聚乙烯、高压低密度聚乙烯和乙烯-乙酸乙烯酯共聚物。
(Ⅱ)至少一层由乙烯和至少一种C3-C18的α-烯烃共聚制得的直链乙烯共聚物,其具有密度从0.916~0.940g/cm3和熔体指数从0.1~10g/10min.。
3、权利要求1的袋,其中该薄膜结构是管式且该袋具有横向热密封端部。
4、权利要求2的袋,具有(Ⅲ)一层密度为0.916g/cm3~0.930g/cm3和熔体指数从0.1~10g/10min.的高压聚乙烯。
5、权利要求2的袋,其中层(Ⅰ)是密封层。
6、权利要求2的袋,其中层(Ⅱ)是外层且层(Ⅰ)是密封层。
7、权利要求3的袋,其中层(Ⅱ)是外层、层(Ⅲ)是芯层且层(Ⅰ)是密封层。
8、权利要求2的袋,其中超低密度聚乙烯具有熔体指数(I2)小于10g/10min.。
9、权利要求1的袋,其中该袋容纳5mL~10L。
10、权利要求1的袋,其中该袋含有牛奶。
11、权利要求1的袋,其中超低密度聚乙烯的I10/I2为0.1~20。
12、权利要求1的袋,其中薄膜结构含有滑爽剂、防粘剂和任选的加工助剂。
13、权利要求1的袋,其中薄膜结构含有颜料,使薄膜结构变得不透光。
14、权利要求1的袋,其中薄膜结构含有紫外线吸收添加剂。
15、权利要求1的袋,其中薄膜结构的α-烯烃是1-丁烯。
16、权利要求1的袋,其中薄膜结构的α-烯烃是1-己烯。
17、权利要求1的袋,其中薄膜结构的α-烯烃是1-辛烯。
18、权利要求1的袋,其中薄膜结构的α-烯烃是至少两种选自1-丁烯、1-己烯和1-辛烯的α-烯烃的混合物。
19、权利要求1的袋,其中高压低密度聚乙烯的熔体强度是在10~40cN的范围。
20、权利要求1的袋,其中高压低密度聚乙烯的熔体强度是在13~25cN的范围。
21、权利要求1的袋,其中聚合物组合物的熔体强度是在5~70cN的范围。
22、用于包装应用的聚合物组合物的薄膜结构,含有:
(A)基于该组合物总重量的10~100wt%的(1)和(2)的混合物:(1)基于100重量份的该混合物,5~95wt%的至少一种超低密度聚乙烯,其为由乙烯和至少一种C3-C18的α-烯烃共聚制得的直链乙烯共聚物,且具有:(a)密度从0.89g/cm3~小于0.916g/cm3,(b)熔体指数(I2)小于10g/10min.,(c)熔体流动比I10/I2大于5,(d)分子量分布,Mw/Mn大于3,(e)由差示扫描量热计测量的峰值熔点大于100℃,和(2)基于100重量份的该混合物,5~95wt%的高压低密度聚乙烯,具有密度从0.916g/cm3~0.93g/cm3,熔体指数(I2)小于约1g/10min.和在190℃用Gottfert Rheotens装置测定的熔体强度大于10cN;和
(B)基于该组合物总重量的0~90wt%的至少一种聚合物,选自直链低密度聚乙烯、高压低密度聚乙烯和乙烯-乙酸乙烯酯共聚物。
23、权利要求22的薄膜结构,其中直链乙烯共聚物的密度为0.916~0.94g/cm3。
24、权利要求22的薄膜结构,其中聚合物组合物的熔体强度是在5~70cN的范围。
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US08/567,608 US5721025A (en) | 1995-12-05 | 1995-12-05 | Pouches for packaging flowable materials in pouches |
US08/567,608 | 1995-12-05 |
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CN1206373A CN1206373A (zh) | 1999-01-27 |
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CN96199357A Expired - Fee Related CN1074986C (zh) | 1995-12-05 | 1996-11-26 | 用于在袋中包装流动性物料的新型袋 |
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US (1) | US5721025A (zh) |
EP (1) | EP0865361B2 (zh) |
JP (1) | JP2000502016A (zh) |
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CN (1) | CN1074986C (zh) |
AR (1) | AR004850A1 (zh) |
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Also Published As
Publication number | Publication date |
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CA2239579A1 (en) | 1997-06-12 |
CA2239579C (en) | 2003-01-07 |
DE69630392T3 (de) | 2008-06-19 |
EP0865361A4 (en) | 1999-09-15 |
KR19990071933A (ko) | 1999-09-27 |
CN1206373A (zh) | 1999-01-27 |
DE69630392D1 (de) | 2003-11-20 |
AU1274197A (en) | 1997-06-27 |
EP0865361B2 (en) | 2007-11-14 |
ZA9610190B (en) | 1998-06-04 |
ES2205071T5 (es) | 2008-04-16 |
BR9611903A (pt) | 1999-03-02 |
EP0865361B1 (en) | 2003-10-15 |
DE69630392T2 (de) | 2004-06-24 |
WO1997020693A1 (en) | 1997-06-12 |
JP2000502016A (ja) | 2000-02-22 |
ES2205071T3 (es) | 2004-05-01 |
AU733517B2 (en) | 2001-05-17 |
EP0865361A1 (en) | 1998-09-23 |
MX9804440A (es) | 1998-12-31 |
AR004850A1 (es) | 1999-03-10 |
US5721025A (en) | 1998-02-24 |
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