CN1074987C - 高模量的薄膜 - Google Patents
高模量的薄膜 Download PDFInfo
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- CN1074987C CN1074987C CN97195481A CN97195481A CN1074987C CN 1074987 C CN1074987 C CN 1074987C CN 97195481 A CN97195481 A CN 97195481A CN 97195481 A CN97195481 A CN 97195481A CN 1074987 C CN1074987 C CN 1074987C
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Abstract
一种包括含有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的层。该薄膜优选基本上不含线性低密度聚乙烯。该薄膜可以是单层或多层的薄膜,且可包括含有密度至少为每立方厘米0.925克的乙烯聚合物的芯层和具有上述混合物的一个或多个外层。也可以包括含有密度小于每立方厘米0.925克的乙烯共聚物的至少一个中间层。该薄膜优选具有的厚度小于0.60密耳;纵向上的收缩力小于0.35磅,横向上的收缩力小于0.30磅;且在纵向上的模量至少为60,000psi,在横向上的模量至少为75,000psi。该薄膜对各种包装用途均可提供优越的特性。
Description
发明领域
本发明涉及可用于包装各种物品的高劲度(高模量)热塑性薄膜。
发明背景
本发明所针对的是一种新型和实用的薄膜。这些薄膜特别是热收缩性薄膜在许多包装应用中是众所周知的。一个实例是W.R.Grace在市场上供应的D-955薄膜。已证明在需要包装薄膜具有高收缩性、优良光学性和其他所需特性的场合,这种薄膜非常适用于各种包装用途。上述这些其他的特性包括耐冲击性、抗引发撕裂和撕裂蔓延性。这类薄膜公开在Schoenberg的美国专利4,551,380和4,643,943中,兹将这两个专利全部引入本文作为参考。
在要求较高劲度即高模量的最终应用中可能希望使用类似D-955的热收缩性材料。这种最终应用的一个实例与某些高速包装机械有关。遗憾的是,这类薄膜的劲度不够,因而不能为上述应用提供最佳的包装材料。
也可能希望提供一种比许多市售薄膜的厚度更薄的材料。这样,由于减少了用于生产薄膜的原料量会使生产费用降低。也可以提供一种由于减少污染源而在环境保护上具有吸引力的薄膜。然而,试图通过简单地减小目前通用薄膜的标准尺寸来达到上述要求,就会发生薄膜的性能降低。这些性能包括如已指出对一些包装用途已处于最低容限或不能接受程度的模量(劲度)、热密封强度以及耐冲击性。
此外,可能希望提供一种比许多市售薄膜的收缩力更低的材料。这种材料适用于待包装产品对高热收缩力敏感,且当这类薄膜围绕该产品热收缩时会使产品变形的包装用途。
发明概述
在一个方面中,本发明的薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的层,所述层基本上不含线性低密度聚乙烯。
在第二方面中,一种多层薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物的芯层;和各自包括具有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的两个外层,至少一个所述外层基本上不含线性低密度聚乙烯。
在第三方面中,一种多层薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物的芯层;至少一种包括具有密度小于每立方厘米0.925克的乙烯共聚物的中间层;和各自包括具有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的两个外层,至少一个所述外层基本上不含线性低密度聚乙烯。
在第四方面中,一种薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的层,所述薄膜具有的厚度小于1.3×10-5m。
在第五方面中,一种主要由一层包括密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物组成的薄膜,所述薄膜具有的厚度小于1.5×10-5m。
在第六方面中,一种薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的层,所述薄膜具有的纵向收缩力小于0.16kg,横向收缩力小于0.14kg。
在第七方面中,一种多层薄膜包括含有密度至少为每立方厘米0.925克的乙烯聚合物的芯层;和各自包括具有密度至少为每立方厘米0.925克的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的两个外层,所述薄膜纵向上具有的模量至少为4.136×108Pa,而在横向上至少为5.171×108Pa。
在第八方面中,一种薄膜包括含有26%-69%的密度至少为每立方厘米0.925克的乙烯聚合物和31%-74%的选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物的层。定义
本文中所用的术语“芯层”系指多层薄膜的中间层。
本文中所用的术语“外层”系指通常是多层薄膜的最外层、经常为表面层,不过,也可将另外的一些层和/或薄膜粘附在其上。
本文中的“聚合物”包括均聚物、共聚物、三元共聚物等。本文中的“共聚物”包括共聚物、三元共聚物等。
本文中所用的所有组分百分数均以“重量”为基准计。
本文中所用的术语“中间层”系指多层薄膜中位于该薄膜的外层和芯层之间的层。
本文中所用的“线性低密度聚乙烯”(LLDPE)具有的密度约为每立方厘米0.916-0.924克。本文中所用的“线性中密度聚乙烯”(LMDPE)具有的密度为每立方厘米0.930至0.939克。本文中所定义的“高密度聚乙烯”(HDPE)具有的密度为每立方厘米0.94克或更大。
本文中所用的术语“乙烯/酯共聚物”(E/E)系指由乙烯和酯例如乙酸乙烯酯、丙烯酸烷基酯或其他单体形成的共聚物,其中,乙烯衍生的单元以主要量存在于该共聚物中,而酯衍生的单元以次要量存在于该共聚物中。
本文中所用的习语“乙烯/α-烯烃共聚物”(EAO)系指像线性中密度聚乙烯(LMDPE)、线性低密度聚乙烯(LLDPE)和很低和超低密度聚乙烯(VLDPE和ULDPE)之类的不均匀材料;以及均相聚合物(HEAO)例如Mitsui Petrochemical Corporation供应的TAFMER(TM)乙烯/α-烯烃共聚物和茂金属催化聚合物例如Exxon供应的EXACT(TM)材料。这些材料通常包括乙烯与一种或多种选自C4-C10α-烯烃例如丁烯-1(即,1-丁烯)、己烯-1、辛烯-1等的共聚单体的共聚物,其中该共聚物的分子包括具有较少侧链支链的长链或交联结构。这种分子结构与比其各自的对应物更高地支化的常规低或中密度聚乙烯不同。其他可从Dow Chemical Company买到的称为AFFINITY(TM)树脂的乙烯/α-烯烃共聚物,例如长链支化的均相乙烯/α-烯烃共聚物也可作为用于本发明的另一类乙烯/α-烯烃共聚物包括在内。
“热收缩性”在本文中定义为当将一种材料加热到高于室温(例如96℃)的适当温度时,该材料在至少一个线性方向上具有5%或更大自由收缩率的特性。
本文中的“基本上不含线性低密度聚乙烯的层”指的是有关层包含小于50%(重量)的LLDPE、且优选小于40%,例如小于30%、20%、10%和5%的LLDPE。更优选在有关层中没有LLDPE存在。已发现,在薄膜中特别是在该薄膜的一个或两个外层中极少或没有LLDPE,导致在包装设备中通过采用本发明而获得良好的性能。
附图简述
图1是本发明优选的三层实施方案的横断面视图。
图2是本发明优选的五层实施方案的横断面视图。
优选的实施方案说明
参看图1,该图是本发明优选的三层实施方案的横断面视图,可以看出,该实施方案包括芯层1和两个外层2和3。优选外层2和3是表面层。
芯层1包括具有密度至少为每立方厘米0.925克(g/cc)的乙烯聚合物、优选具有C4-C10共聚单体的乙烯/α-烯烃共聚物、更优选线性中密度聚乙烯。该芯层也可以包括例如高密度聚乙烯。除乙烯聚合物以外,在该芯层中还可以包括其他的聚合物材料。这些其他材料的实例是密度小于0.925g/cc的乙烯聚合物或共聚物,例如LLDPE或VLDPE;乙烯/酯共聚物,例如乙烯/乙烯基酯共聚物例如乙烯/乙酸乙烯酯共聚物,或乙烯/丙烯酸烷基酯共聚物,例如乙烯/丙烯酸乙酯共聚物、乙烯/丙烯酸甲酯共聚物或乙烯/丙烯酸丁酯共聚物;或乙烯/酸共聚物,例如乙烯/丙烯酸共聚物或乙烯/甲基丙烯酸共聚物。也可以按这些材料任一相互比例的混合物和/或与具有密度至少为0.925g/cc的乙烯聚合物一起使用。
外层2和3包括或主要由具有密度至少为0.925g/cc的乙烯聚合物和选自乙烯/酯共聚物以及乙烯/α-烯烃共聚物的乙烯共聚物的混合物组成。
具有密度至少为0.925g/cc的乙烯聚合物可以是任一种适用于芯层1的材料。也可以采用任一比例的这些材料的混合物。
乙烯/酯共聚物优选的是乙烯乙酸乙烯酯共聚物、乙烯丙烯酸烷基酯共聚物或本文中公开的任一种适用于该芯层的材料。
乙烯/α-烯烃共聚物优选包括乙烯和C4-C10共聚单体的共聚物。优选均相乙烯/α-烯烃共聚物或具有密度小于0.916g/cc的乙烯/α-烯烃共聚物。
外层2和3的混合物优选的是26%-69%、更优选30%-65%、例如40%-60%或50%的具有密度至少为0.925g/cc的乙烯聚合物和31%-74%、更优选35%-60%、例如45%-55%或50%的乙烯/酯共聚物和/或乙烯/α-烯烃共聚物的混合物。
参看图2,该图是本发明优选的五层实施方案的横断面视图,可以看出,该实施方案包括芯层11、两个中间层12和13以及两个外层14和15。优选外层14和15是表面层。
芯层11包括任一种上述用于芯层1的材料。
外层12和13包括任一种上述用于外层2和3的材料。
中间层14和15可以包括使芯层11粘附在外层12和13上的任一种材料。这可以包括聚合型粘合剂例如酐接枝的聚合物例如酐接枝的LLDPE;乙烯/α-烯烃共聚物例如LLDPE、极低密度聚乙烯、均相乙烯/α-烯烃共聚物、及其混合物;或甚至是常规的粘合剂例如聚氨酯。层14和15也可以包括乙烯/酯共聚物,例如乙烯/乙烯基酯共聚物例如乙烯/乙酸乙烯酯共聚物,或乙烯/丙烯酸烷基酯共聚物例如乙烯/丙烯酸乙酯共聚物、乙烯/丙烯酸甲酯共聚物或乙烯/丙烯酸丁酯共聚物;或乙烯/酸共聚物例如乙烯/丙烯酸共聚物或乙烯/甲基丙烯酸共聚物。
通过参阅以下给出的实施例可以进一步理解本发明。这些薄膜可以采用常规的流延共挤塑、层压或其他适宜的方法制成。如果需要,可以采用辐射或化学方法将这些薄膜部分地或全部地交联。如果需要用于给定的最终用途,可以采用截留气泡(trapped bubble)、绷架或其他适宜的方法将这些薄膜定向。其后,可任选将其退火。薄膜的最终厚度可随所用的方法、最终用途等变化。通常的厚度为2.5×10-6~5.1×10-4m。
可以采用任一种常规的方法实现辐射交联。采用辐射法时,将该薄膜进行可使被辐射材料的分子之间诱发交联的高能辐射处理,例如电晕放电、等离子体、火焰、紫外线、X-射线、γ-射线、β-射线以及高能电子束处理。聚合物薄膜的辐射公开在Bornstein等人的美国专利4,064,296中,兹将其全部引入本文作为参考。Bornstein等人公开了采用电离辐射法交联含在该薄膜中的聚合物。在本文中,以辐射单位”RAD”术语表示辐射剂量,一百万RAD也称之为兆拉德,表示为”MR”,或以辐射单位千戈瑞(kGy)术语表示,本领域的技术人员熟知10千戈瑞相当于1MR。适宜的高能电子辐射剂量为至多约10-200kGy、更优选约为15-190kGy、且更优选为20-180kGy。优选采用电子加速器进行辐射,且采用标准的剂量学方法测定剂量水平。也可以采用其他的加速器例如Vander Graff或谐振变压器。该辐射不限于来自加速器的电子,因为任一种电离辐射均可采用。电离辐射可使薄膜中的聚合物交联。更优选的辐射量取决于薄膜及其最终用途。
表1确定了用于实施例中的材料。其余各表说明采用这些材料制成的薄膜特性。
表1
PE1=LLDPE,具有密度为0.920g/cc的乙烯/1-辛烯共聚物,且辛烯-1共聚单体的含量为6.5%。PE2=LMDPE,具有密度为0.935g/cc的乙烯/1-辛烯共聚物,且辛烯-1共聚单体的含量为2.5%。PE3=具有密度为0.912g/cc的乙烯/1-辛烯共聚物。PE4=具有密度为0.902g/cc的乙烯/1-辛烯三元共聚物。EV1=具有3.3%乙酸乙烯酯单体的乙烯/乙酸乙烯酯共聚物。EV2=具有13.3%乙酸乙烯酯共聚单体的乙烯/乙酸乙烯酯共聚物。EV3=具有19%乙酸乙烯酯共聚单体的乙烯/乙酸乙烯酯共聚物。
材料 | 商品名称 | 来源 |
PE1 | DowlexTM 2045.04 | Dow |
PE2 | DowlexTM 2037 | Dow |
PE3 | ||
PE4 | SLP-8-6031 | Exxon |
EV1 | PE 1335 | Rexene |
EV2 | LD-705.15 | Exxon |
EV3 | LD-720.92 | Exxon |
在表2和3中,公开了本发明的十四种五层薄膜结构。这些薄膜结构各自采用复合挤压数层的方法制成,且各具有如下结构:A/B/C/B/A
各层的厚度比为:
A层 | B层 | C层 | B层 | A层 |
2.0 | 1.5 | 3.0 | 1.5 | 2.0 |
除实施例14以外,所有的薄膜均分别在机器中按5×6和横向进行双轴定向。实施例14按5×5之比定向。除在约65kGy下辐照的实施例1以外,所有的薄膜均在80-95kGy的吸收剂量下进行辐照。该薄膜的B层是PE1。该薄膜的C层是PE2。该薄膜的A层是50%PE2、20%的具有90%PE2和10%润滑涂料和防粘添加剂的母料以及30%的一种表1中标明的材料的混合物,各实施例的参数确定在下面的表中。
表2
a=ASTM D 882 g=ASTM D 3420b=ASTM D 882 h=ASTM D 3763c=ASTM D 882 i=ASTM D 1003-61d=ASTM D 1938-67 j=ASTM D 1003-61e=ASTM D 2732 k=ASTM D 2457-70f=ASTM D 2838-81 l=ASTM D 1894*=封闭的(blocked)
物理特性 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 |
薄膜厚度(规格) | 33 | 30 | 30 | 30 | 30 | 30 | |
“A”层中的第三组分 | EV1 | EV1 | EV1 | EV2 | PE4 | EV3 | |
拉伸断裂a |
(Pa×107) | |||||||
LD | 12.0 | 10.1 | 12.9 | 12.3 | 13.0 | 11.9 | |
TD | 17.4 | 13.5 | 14.1 | 14.3 | 15.6 | 14.3 | |
断裂伸长率b(%) | |||||||
LD | 107 | 85 | 111 | 120 | 108 | 88 | |
TD | 62 | 47 | 59 | 69 | 59 | 53 | |
模量c(Pa×107) | |||||||
LD | 65.1 | 64.7 | 69.0 | 59.7 | 57.8 | 55.6 | |
TD | 72.1 | 79.4 | 72.0 | 70.1 | 63.9 | 66.4 | |
撕裂蔓延d(gms) | |||||||
LD | 3 | 4 | 3 | 3 | 3 | 3 | |
TD | 2 | 2 | 2 | 2 | 2 | 2 | |
自由收缩率e(%) | |||||||
200°F下,LD | 8 | 5 | 6 | 7 | 6 | 7 | |
TD | 9 | 9 | 9 | 8 | 11 | 11 | |
220°F下,LD | 12 | 10 | 12 | 12 | 10 | 13 | |
TD | 17 | 16 | 17 | 16 | 18 | 21 | |
240°F下,LD | 32 | 29 | 32 | 32 | 29 | 28 | |
TD | 40 | 39 | 40 | 39 | 39 | 38 | |
260°F下,LD | 78 | 77 | 78 | 78 | 77 | 78 | |
TD | 81 | 81 | 82 | 82 | 81 | 81 | |
280°F下,LD | 78 | 78 | 78 | 78 | 78 | 78 | |
TD | 82 | 81 | 82 | 81 | 82 | 82 | |
300°F下,LD | 78 | 78 | 78 | 78 | 77 | 78 | |
TD | 83 | 82 | 82 | 82 | 82 | 82 |
收缩力f(kg) | |||||||
200°F下,LD | 0.04 | 0.04 | 0.04 | 0.03 | 0.04 | 0.04 | |
TD | 0.085 | 0.085 | 0.077 | 0.077 | 0.091 | 0.091 | |
220°F下,LD | 0.050 | 0.04 | 0.04 | 0.03 | 0.050 | 0.04 | |
TD | 0.10 | 0.095 | 0.095 | 0.09 | 0.099 | 0.11 | |
240°F下,LD | 0.059 | 0.045 | 0.045 | 0.054 | 0.059 | 0.054 | |
TD | 0.11 | 0.099 | 0.095 | 0.11 | 0.11 | 0.059 | |
260°F下,LD | 0.059 | 0.050 | 0.050 | 0.059 | 0.059 | 0.054 | |
TD | 0.11 | 0.09 | 0.095 | 0.099 | 0.10 | 0.095 | |
钢球式顶破冲击g(cm-kg) | 7 | 6 | 6 | 5 | 9 | 9 | |
用测量仪的冲击h(lb) | 7 | 5 | 5 | 7 | 8 | 9 | |
雾度i(%) | 2.8 | 2.9 | 2.6 | 4.6 | 2.1 | 5.8 | |
清晰度j(%) | 66 | 88 | 88 | 80 | 88 | 80 | |
光泽k45° | 83 | 84 | 83 | 70 | 81 | 63 | |
C.O.F.l(in/in) | * | * | * | * | * | * | |
C.O.F.(out/out) | 0.34 | 0.34 | 0.37 | 0.36 | 0.38 | 0.32 |
表3
物理特性 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 实施例12 | 实施例13 | 实施例14 |
薄膜厚度(规格) | 40 | 60 | 45 | 45 | 40 | 45 | 60 |
“A”层中的第三组分 | EV1 | EV1 | EV1 | EV1 | PE4 | PE4 | PE4 |
拉伸断裂Pa×107 | |||||||
LD | 11.99 | 12.7 | 14.3 | 13.4 | 12.9 | 10.9 | 13.5 |
TD | 14.8 | 14.9 | 16.1 | 20.3 | 12.2 | 13.5 | 14.9 |
断裂伸长率(%) | |||||||
LD | 128 | 110 | 113 | 107 | 103 | 110 | 116 |
TD | 59 | 92 | 68 | 58 | 96 | 80 | 91 |
模量Pa×107 | |||||||
LD | 54.4 | 51.3 | 55.5 | 54.5 | 54.2 | 49.5 | 53.2 |
TD | 77.6 | 59.6 | 65.2 | 79.7 | 47.9 | 59.9 | 62.2 |
撕裂蔓延(gms) | |||||||
LD | 4 | 5 | 5 | 5 | 4 | 5 | 7 |
TD | 2 | 4 | 3 | 4 | 3 | 3 | 5 |
自由收缩率(%) | |||||||
200°F下,LD | 7 | 8 | 8 | 9 | 6 | 6 | 7 |
TD | 12 | 13 | 11 | 13 | 11 | 12 | 14 |
220°F下,LD | 10 | 15 | 14 | 14 | 12 | 12 | 13 |
TD | 20 | 23 | 21 | 21 | 21 | 20 | 23 |
240°F下,LD | 28 | 32 | 33 | 34 | 37 | 44 | 51 |
TD | 38 | 42 | 43 | 44 | 48 | 54 | 58 |
260°F下,LD | 77 | 77 | 78 | 78 | 77 | 77 | 78 |
TD | 82 | 79 | 82 | 80 | 80 | 81 | 80 |
280°F下,LD | 78 | 78 | 78 | 78 | 77 | 77 | 78 |
TD | 81 | 80 | 81 | 81 | 80 | 82 | 80 |
300°F下,LD | 79 | 78 | 79 | 78 | 78 | 78 | 78 |
TD | 82 | 80 | 82 | 82 | 82 | 82 | 80 |
收缩力(磅) | |||||||
200°F下,LD | 0.03 | 0.03 | 0.050 | 0.059 | 0.03 | 0.045 | 0.054 |
TD | 0.11 | 0.16 | 0.12 | 0.12 | 0.10 | 0.10 | 0.14 |
220°F下,LD | 0.045 | 0.091 | 0.063 | 0.072 | 0.045 | 0.036 | 0.076 |
TD | 0.13 | 0.19 | 0.15 | 0.14 | 0.13 | 0.12 | 0.16 |
240°F下,LD | 0.058 | 0.11 | 0.076 | 0.086 | 0.059 | 0.045 | 0.035 |
TD | 0.14 | 0.18 | 0.18 | 0.15 | 0.13 | 0.13 | 0.18 |
260°F下,LD | 0.054 | 0.11 | 0.072 | 0.081 | 0.059 | 0.068 | 0.033 |
TD | 0.12 | 0.17 | 0.16 | 0.15 | 0.12 | 0.13 | 0.16 |
钢球式顶破冲击(cm-kg) | 14 | 12 | 21 | 18 | 14 | 15 | 18 |
用测量仪的冲击(lb) | 9 | 16 | 17 | 15 | 11 | 11 | 17 |
雾度(%) | 2.8 | 3.2 | 3.1 | 3.2 | 3.4 | 3.4 | 3.6 |
清晰度(%) | 66 | 87 | 87 | 87 | 87 | 87 | 86 |
光泽,45° | 86 | 86 | 85 | 86 | 77 | 74 | 82 |
C.O.F.(in/in) | * | * | * | * | * | * | * |
C.O.F.(out/out) | 0.33 | 0.35 | 0.31 | 0.29 | 0.34 | 0.31 | 0.30 |
*=封闭的。
在表4中,公开了本发明的五种另外的五层薄膜结构。这些薄膜结构各自采用复合挤压数层的方法制成,且各具有如下结构:A/B/C/B/A
各层的厚度比为:
A层 | B层 | C层 | B层 | A层 |
1 | 1 | 1 | 1 | 1 |
实施例15-19的所有厚度均为30标准尺寸(0.30密耳)。实施例15、16和17的薄膜均分别在纵向和横向上按5×6双轴定向。实施例18和19按5.5×5.5之比定向。除在约78kGy下辐照的实施例15以外,所有的薄膜均在61kGy的吸收剂量下进行辐照。该薄膜的B层是PE1。该薄膜的C层是PE2。该薄膜的A层是PE2、具有90%PE2和10%润滑涂料和防粘添加剂的母料(MB)以及EV1或PE4的混合物。各实施例的A层配方确定在下面的表中。
表4
实施例15 | 实施例16 | 实施例17 | 实施例18 | 实施例19 |
50%PE2+10%PE2MB+40%EV1 | 50%PE2+10%PE2MB+40%EV1 | 40%PE2+10%PE2MB+50%EV1 | 50%PE2+10%PE2MB+40%PE4 | 40%PE2+10%PE2MB+50%PE4 |
在表5中,公开了本发明的五种三层薄膜结构。这些薄膜结构各自采用复合挤压数层的方法制成,且各具有如下结构:A/B/A
各层的厚度比为:
A层 | C层 | A层 |
1 | 3 | 1 |
实施例20-24的所有薄膜都经过辐照,且分别在机器中按5×5(对实施例20为5.5×5.5)和横向进行双轴定向。实施例20-24薄膜的C层都是60%PE1和40%PE2的混合物。实施例20-24薄膜的A层都是40%PE2、20%的具有86%PE2和14%润滑涂料和防粘添加剂的母料以及40%的一种表1中标明的材料的混合物,各实施例的参数确定在下面的表中。一种对比薄膜,对比例1,代表具有A/B/A结构的D-955,各层的厚度比为1/2/1,且B包括PE1,A包括50%LLDPE、25%LMDPE以及25%的包括90%EVA和10%润滑涂料和防粘添加剂的母料的混合物。
表5
物理特性 | 对比例1 | 实施例20 | 实施例21 | 实施例22 | 实施例23 | 实施例24 |
薄膜厚度(规格) | 60 | 30 | 40 | 30 | 30 | 40 |
“A”层中的第三组分 | -- | EV1 | EV1 | EV1 | PE4 | PE4 |
拉伸断裂Pa×107 | ||||||
LD | 12.9 | 12.6 | 12.0 | 12.7 | 13.1 | 14.6 |
TD | 15.4 | 14.1 | 13.1 | 13.9 | 14.2 | 14.5 |
断裂伸长率(%) | ||||||
LD | 107 | 90 | 97 | 97 | 110 | 112 |
TD | 81 | 107 | 117 | 85 | 75 | 97 |
模量Pa×107 | ||||||
LD | 38.6 | 69.6 | 56.6 | 57.3 | 47.7 | 48.1 |
TD | 48.8 | 72.4 | 56.2 | 64.3 | 59.4 | 53.7 |
撕裂蔓延(gms) | ||||||
LD | 5 | 2 | 3 | 2 | 2 | 3 |
TD | 5 | 2 | 3 | 2 | 3 | 4 |
自由收缩率(%) |
220°下,LD | 24 | 14 | 18 | 18 | 19 | 21 |
TD | 34 | 24 | 27 | 24 | 27 | 30 |
240°下,LD | 59 | 40 | 44 | 43 | 52 | 53 |
TD | 63 | 49 | 50 | 52 | 58 | 59 |
260°下,LD | 79 | 81 | 79 | 79 | 80 | 79 |
TD | 79 | 73 | 78 | 79 | 78 | 78 |
280°下,LD | 79 | 81 | 79 | 80 | 80 | 79 |
TD | 80 | 82 | 81 | 79 | 80 | 78 |
用测量仪的冲击(lb) | 20 | 7 | 12 | 8 | 6 | 9 |
雾度(%) | 3.6 | 4.2 | 5.4 | 4.5 | 4.6 | 4.4 |
清晰度(%) | 79 | 86 | 84 | 86 | 86 | 86 |
光泽,45° | 86 | 76 | 78 | 80 | 77 | 80 |
本发明另外的薄膜结构列于下面的表6中。如实施例25-34中的这些薄膜可以是单层薄膜或包括所示结构的多层薄膜。
表6
实施例 | 薄膜结构 |
25 | 10%LMDPE+90%EVA |
26 | 30%LMDPE+70%EVA |
27 | 50%LMDPE+50%EVA |
28 | 70%LMDPE+30%EVA |
29 | 90%LMDPE+10%EVA |
30 | 10%LMDPE+90%HEAO |
31 | 30%LMDPE+70%HEAO |
32 | 50%LMDPE+50%HEAO |
33 | 70%LMDPE+30%HEAO |
34 | 90%LMDPE+10%HEAO |
35 | 10%LMDPE+90%EVA/LMDPE/10%LMDPE+90%EVA |
36 | 30%LMDPE+70%EVA/LMDPE/30%LMDPE+70%EVA |
37 | 50%LMDPE+50%EVA/LMDPE/50%LMDPE+50%EVA |
38 | 70%LMDPE+30%EVA/LMDPE/70%LMDPE+30%EVA |
39 | 90%LMDPE+10%EVA/LMDPE/90%LMDPE+10%EVA |
40 | 10%LMDPE+90%HEAO/LMDPE/10%LMDPE+90%HEAO |
41 | 30%LMDPE+70%HEAO/LMDPE/30%LMDPE+70%HEAO |
42 | 50%LMDPE+50%HEAO/LMDPE/50%LMDPE+50%HEAO |
43 | 70%LMDPE+30%HEAO/LMDPE/70%LMDPE+30%HEAO |
44 | 90%LMDPE+10%HEAO/LMDPE/90%LMDPE+10%HEAO |
45 | 10%LMDPE+90%EVA/LLDPE/LMDPE/LLDPE/10%LMDPE+90%EVA |
46 | 30%LMDPE+70%EVA/LLDPE/LMDPE/LLDPE/30%LMDPE+70%EVA |
47 | 50%LMDPE+50%EVA/LLDPE/LMDPE/LLDPE/50%LMDPE+50%EVA |
48 | 70%LMDPE+30%EVA/LLDPE/LMDPE/LLDPE/70%LMDPE+30%EVA |
49 | 90%LMDPE+10%EVA/LLDPE/LMDPE/LLDPE/90%LMDPE+10%EVA |
50 | 10%LMDPE+90%HEAO/LLDPE/LMDPE/LLDPE/10%LMDPE+90%HEAO |
51 | 30%LMDPE+70%HEAO/LLDPE/LMDPE/LLDPE/30%LMDPE+70%HEAO |
52 | 50%LMDPE+50%HEAO/LLDPE/LMDPE/LLDPE/50%LMDPE+50%HEAO |
53 | 70%LMDPE+30%HEAO/LLDPE/LMDPE/LLDPE/70%LMDPE+30%HEAO |
54 | 90%LMDPE+10%HEAO/LLDPE/LMDPE/LLDPE/90%LMDP+10%HEAO |
55 | 10%HDPE+90%EVA/HDPE/10%HDPE+90%EVA |
56 | 30%HDPE+70%EVA/HDPE/30%HDPE+70%EVA |
57 | 50%HDPE+50%EVA/HDPE/50%HDPE+50%EVA |
58 | 70%HDPE+30%EVA/HDPE/70%HDPE+30%EVA |
59 | 90%HDPE+10%EVA/HDPE/90%HDPE+10%EVA |
60 | 10%HDPE+90%HEAO/HDPE/10%HDPE+90%HEAO |
61 | 30%HDPE+70%HEAO/HDPE/30%HDPE+70%HEAO |
62 | 50%HDPE+50%HEAO/HDPE/50%HDPE+50%HEAO |
63 | 70%HDPE+30%HEAO/HDPE/70%HDPE+30%HEAO |
64 | 90%HDPE+10%HEAO/HDPE/90%HDPE+10%HEAO |
65 | 10%HDPE+90%EVA/LLDPE/HDPE/LLDPE/10%HDPE+90%EVA |
66 | 30%HDPE+70%EVA/LLDPE/HDPE/LLDPE/30%HDPE+70%EVA |
67 | 50%HDPE+50%EVA/LLDPE/HDPE/LLDPE/50%HDPE+50%EVA |
68 | 70%HDPE+30%EVA/LLDPE/HDPE/LLDPE/70%HDPE+30%EVA |
69 | 90%HDPE+10%EVA/LLDPE/HDPE/LLDPE/90%HDPE+10%EVA |
70 | 10%HDPE+90%HEAO/LLDPE/HDPE/LLDPE/10%HDPE+90%HEAO |
71 | 30%HDPE+70%HEAO/LLDPE/HDPE/LLDPE/30%HDPE+70%HEAO |
72 | 50%HDPE+50%HEAO/LLDPE/HDPE/LLDPE/50%HDPE+50%HEAO |
73 | 70%HDPE+30%HEAO/LLDPE/HDPE/LLDPE/70%HDPE+30%HEAO |
74 | 90%HDPE+10%HEAO/LLDPE/HDPE/LLDPE/90%HDPE+10%HEAO |
本发明的一些薄膜具有较低的收缩力,因而特别适用于包装敏感产品的“软收缩”用途。
这是因为,虽然本发明的这类薄膜可以具有类似于较厚规格薄膜的收缩张力,但由于其结构较薄因而收缩力相当小。
本发明的薄膜优选的收缩力值在纵向上小于0.35、优选小于0.30,例如小于0.25、0.20、0.15和0.10;在横向上小于0.30、优选小于0.25、0.20、0.15和0.10。
在表7中,将本发明的三种另外的三层薄膜与表中标明“对比例2”的对照,D-955薄膜,进行比较。对比例2的组成和结构与表5中对比例1的相同。这些薄膜各自采用复合挤压数层的方法制成,且各具有如下结构:A/B/A
各层的厚度比为:
A层 | B层 | A层 |
1 | 3 | 1 |
所有的薄膜均分别在机器中按5×6和横向进行双轴定向。所有的薄膜均在20-80kGy的吸收剂量下进行辐照。该薄膜的B层是60%PE1和40%PE2的混合物。该薄膜的A层与表7中各实施例的相同。该母料包括90%PE2和10%润滑涂料以及防粘添加剂。
表7
75 | 45%PE2+40%PE4+15%母料 |
76 | 45%PE2+40%PE4+15%母料 |
77 | 40%PE2+40%EV1+20%母料 |
表8
物理特性 | 对比例2 | 实施例75 | 实施例76 | 实施例77 |
薄膜厚度(规格) | 60 | 30 | 30 | 30 |
模量cPa×107 | ||||
LD | 49.7 | 53.6 | 49.5 | 57.0 |
TD | 48.8 | 64.9 | 49.0 | 58.7 |
自由收缩率e(%) | ||||
220°F下,LD | 34 | 20 | 28 | 25 |
TD | 40 | 28 | 33 | 32 |
240°F下,LD | 64 | 43 | 55 | 48 |
TD | 63 | 50 | 56 | 53 |
260°F下,LD | 82 | 80 | 80 | 81 |
TD | 76 | 80 | 76 | 78 |
收缩张力fPa×104 | ||||
260°F下,LD | 419 | 329 | 374 | 349 |
TD | 281 | 349 | 413 | 361 |
收缩力f(磅) | ||||
220°F下,LD | 0.16 | 0.045 | 0.063 | 0.063 |
TD | 0.14 | 0.081 | 0.076 | 0.081 |
240°F下,LD | 0.17 | 0.063 | 0.072 | 0.072 |
TD | 0.14 | 0.081 | 0.081 | 0.085 |
260°F下,LD | 0.18 | 0.068 | 0.085 | 0.081 |
TD | 0.12 | 0.077 | 0.077 | 0.077 |
本发明的薄膜可以具有的厚度为2.5×10-6m至3.8×10-4m,然而优选的厚度小于5.1×10-5m、优选小于3.8×10-5m例如2.5×10-5m,且更优选小于1.8×10-5m。更优选该薄膜的厚度小于1.5×10-5m,例如1.4×10-5、1.3×10-5、1.1×10-5、1.0×10-5、8.9×10-6、7.6×10-6和6.4×10-6m厚。
本发明的薄膜可以具有的模量优选在纵向(LD)上至少为4.1×108Pa.更优选该量在LD上至少为4.5×108Pa、更优选至少为4.8×108Pa,例如5.2×108Pa、5.5×108Pa、6.2×108Pa、6.5×108Pa、6.9×108Pa和更高。优选的范围在LD上为4.1×108-6.9×108Pa、更优选4.5×108-6.5×108Pa,更优选4.8×108-6.2×108Pa,例如5.2×108-5.9×108Pa。模量值高于8.3×108Pa时,该薄膜仍然实用,然而薄膜的抗撕裂特性会显著降低。
本发明原薄膜可以具有的模量优选在横向(TD)上至少为5.2×108Pa。更优选该模量在TD上至少为5.5×108Pa、更优选至少为5.9×108Pa,例如6.2×108Pa、6.5×108Pa、6.9×108Pa、7.2×108Pa、7.6×108Pa、7.9×108Pa和6.2×108Pa。优选的范围在TD上为5.2×108-8.3×108Pa、更优选5.5×108-7.9×108Pa、更优选5.9×108-7.6×108Pa,例如6.2×108-8.3×109Pa、更优选5.5×108-7.9×108Pa、更优选5.9×108-7.6×108Pa,例如6.2×108-7.2×108Pa和6.5×108-6.9×108Pa。
模量太低,在某些高速包装设备中使用该薄膜、特别是本发明薄膜的较薄实施方案时会导致困难。模量太高,会导致更大的撕裂蔓延趋势。
本发明的薄膜可以具有任何适宜的层数;可以是单层薄膜,或具有2、3、4、5、6、7、8、9或更多层。这些薄膜在结构上可以是对称的或不对称的。例如,本发明的薄膜可以具有以下结构之一:LMDPE/LMDPE+EVALMDPE+EVA/LMDPE/LLDPE/LMDPE+EVALMDPE/LMDPE+HEAOLMDPE+HEAO/LMDPE/LLDPE/LMDPE+HEAOHDPE/HDPE+EVAHDPE+EVA/HDPE/LLDPE/HDPE+EVAHDPE/HDPE+HEAOHDPE+HEAO/HDPE/LLDPE/HDPE+HEAO
层的规格可以不同,甚至各层之间可以具有类似的组成。
本发明的薄膜可以采用不同的材料作为外层或中间层,因此,例如两个“A”层在组成、交联度、厚度或其他参数上可以彼此不同。因此,A结构例如70%LMDPE+30%EVA/LLDPE/LMDPE/VLDPE/90%HDPE+10%HEAO属于本发明的范围。
如果要定向,该薄膜可按单轴向或双轴向定向。在各方向上的定向比例优选为2∶1-10∶1、更优选为2.5∶1-9∶1,例如3∶1-8∶1、4∶1-7∶1、4.5∶1-6∶1和5.5∶1。
Claims (10)
1.一种多层薄膜,该薄膜包括:
a)包括具有密度至少为每立方厘米0.925克的乙烯聚合物的芯层;和
b)各自包括以下混合物的两个外层:
ⅰ)具有密度至少为每立方厘米0.930克的乙烯聚合物,和
ⅱ)选自乙烯/C4-C10α-烯烃共聚物和乙烯/酯共聚物的乙烯共聚物;
其中至少一个外层包含少于30%的线性低密度聚乙烯;密度为至少0.930g/cm3的乙烯聚合物,构成两层各自的共混物的40-69%,其中所述膜的弹性模量纵向上至少为4.1×108Pa,在横向上至少为5.2×108Pa。
2.权利要求1的薄膜,其中芯层的具有密度至少为每立方厘米0.925克的乙烯聚合物选自线性中密度聚乙烯和高密度聚乙烯。
3.权利要求1的薄膜,其中该乙烯共聚物选自乙烯/酯共聚物和均相乙烯/α-烯烃共聚物。
4.权利要求1的薄膜,其中该薄膜是交联了的。
5.权利要求1的薄膜,其中该薄膜是取向了的。
6.权利要求1的薄膜,其中该薄膜是热收缩性的。
7.权利要求1的薄膜,其中该薄膜具有的厚度小于1.5×10-5m。
8.权利要求1的薄膜,该薄膜还包括至少一个放置在芯层和外层之间的中间层,该中间层包括密度小于每立方厘米0.925克的乙烯共聚物。
9.权利要求1的薄膜,其中至少一个外层的乙烯聚合物具有至少0.930g/cm3密度,并选自线性中密度聚乙烯和高密度聚乙烯。
10.权利要求1的薄膜,其中薄膜厚度小于1.3×10-5m。
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EP4357134A1 (en) * | 2022-10-18 | 2024-04-24 | Dow Global Technologies LLC | Oriented multilayer film including metal layer |
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WO1994006857A1 (en) * | 1992-09-16 | 1994-03-31 | Exxon Chemical Patents Inc. | Soft films having enhanced physical properties |
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1996
- 1996-04-12 US US08/631,442 patent/US5897941A/en not_active Expired - Lifetime
-
1997
- 1997-04-04 CN CN97195481A patent/CN1074987C/zh not_active Expired - Fee Related
- 1997-04-04 ES ES97920144T patent/ES2180978T3/es not_active Expired - Lifetime
- 1997-04-04 DE DE69730058T patent/DE69730058T2/de not_active Expired - Lifetime
- 1997-04-04 AT AT97920144T patent/ATE223308T1/de not_active IP Right Cessation
- 1997-04-04 EP EP02016079A patent/EP1251002B1/en not_active Expired - Lifetime
- 1997-04-04 AT AT02016079T patent/ATE284789T1/de not_active IP Right Cessation
- 1997-04-04 BR BR9708657A patent/BR9708657A/pt not_active IP Right Cessation
- 1997-04-04 DE DE69731990T patent/DE69731990T2/de not_active Expired - Lifetime
- 1997-04-04 EP EP01101349A patent/EP1110715B1/en not_active Expired - Lifetime
- 1997-04-04 AT AT01101349T patent/ATE271971T1/de not_active IP Right Cessation
- 1997-04-04 DE DE69715179T patent/DE69715179T2/de not_active Expired - Lifetime
- 1997-04-04 AU AU24410/97A patent/AU723591B2/en not_active Ceased
- 1997-04-04 NZ NZ332182A patent/NZ332182A/xx not_active IP Right Cessation
- 1997-04-04 EP EP97920144A patent/EP0892719B1/en not_active Expired - Lifetime
- 1997-04-04 WO PCT/US1997/005644 patent/WO1997038857A1/en not_active Application Discontinuation
- 1997-04-04 JP JP53715297A patent/JP3483576B2/ja not_active Expired - Lifetime
- 1997-04-04 KR KR1019980708069A patent/KR20000005349A/ko not_active Application Discontinuation
- 1997-04-04 PT PT97920144T patent/PT892719E/pt unknown
- 1997-04-04 CA CA002251682A patent/CA2251682C/en not_active Expired - Fee Related
- 1997-04-08 ZA ZA9702982A patent/ZA972982B/xx unknown
- 1997-04-11 CO CO97018804A patent/CO4820404A1/es unknown
- 1997-04-11 AR ARP970101459A patent/AR006615A1/es unknown
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2003
- 2003-01-28 JP JP2003018314A patent/JP3977754B2/ja not_active Expired - Fee Related
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US5206075A (en) * | 1991-12-19 | 1993-04-27 | Exxon Chemical Patents Inc. | Sealable polyolefin films containing very low density ethylene copolymers |
WO1994006857A1 (en) * | 1992-09-16 | 1994-03-31 | Exxon Chemical Patents Inc. | Soft films having enhanced physical properties |
Also Published As
Publication number | Publication date |
---|---|
DE69715179D1 (de) | 2002-10-10 |
KR20000005349A (ko) | 2000-01-25 |
NZ332182A (en) | 2000-03-27 |
DE69731990D1 (de) | 2005-01-20 |
EP0892719B1 (en) | 2002-09-04 |
US5897941A (en) | 1999-04-27 |
ES2180978T3 (es) | 2003-02-16 |
ATE223308T1 (de) | 2002-09-15 |
AR006615A1 (es) | 1999-09-08 |
DE69715179T2 (de) | 2003-01-02 |
CA2251682C (en) | 2004-06-08 |
EP1110715A1 (en) | 2001-06-27 |
CA2251682A1 (en) | 1997-10-23 |
PT892719E (pt) | 2003-01-31 |
WO1997038857A1 (en) | 1997-10-23 |
JP3977754B2 (ja) | 2007-09-19 |
DE69730058D1 (de) | 2004-09-02 |
EP0892719A1 (en) | 1999-01-27 |
JP2004001384A (ja) | 2004-01-08 |
JP3483576B2 (ja) | 2004-01-06 |
ATE284789T1 (de) | 2005-01-15 |
EP1110715B1 (en) | 2004-07-28 |
DE69731990T2 (de) | 2005-12-29 |
ZA972982B (en) | 1997-11-03 |
EP1251002A1 (en) | 2002-10-23 |
BR9708657A (pt) | 1999-08-03 |
DE69730058T2 (de) | 2005-07-21 |
AU2441097A (en) | 1997-11-07 |
AU723591B2 (en) | 2000-08-31 |
JP2001500073A (ja) | 2001-01-09 |
EP1251002B1 (en) | 2004-12-15 |
CO4820404A1 (es) | 1999-07-28 |
CN1222115A (zh) | 1999-07-07 |
ATE271971T1 (de) | 2004-08-15 |
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