CN1084452A - 防湿薄膜 - Google Patents
防湿薄膜 Download PDFInfo
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Abstract
一种用于防湿包装应用的多层薄膜,具有至少一
个包含丙烯聚合物或共聚物与烃树脂掺混物的层和
两个另外的包含丙烯聚合物或共聚物、乙烯、α-烯烃
共聚物、离聚物、聚丁烯或它们的掺混物的层。在某
些例子中可包含具有乙烯、乙烯醇共聚物或其它阻氧
材料或高密度聚乙烯的芯层。该多层薄膜的一个优
选例显示出优良的防湿和光学特性及收缩性能(当该
薄膜已经取向时)。在包含EVOH或其它阻氧材料
的例子中高阻氧也是一个特征。
Description
本发明涉及的是包装用热塑性塑料薄膜,尤其本发明涉及具有高防湿性能的多层薄膜。
热塑性塑料(尤其是聚烯烃材料)薄膜在包装各种制品(包括食品)方面已经使用了相当长时间了,这些制品需要能防止环境污染、有醒目的外观和防止在储存、分发过程中误用。此外还需要有合适的光学性能,以便在包装后在分发过程中和最后在销售时提供包装产品的检验。将光学性能(例如高光泽、高清晰度和低雾度特征)赋予给漂亮醒目的包装材料和包装产品,提高了产品对顾客的吸引力。
各种聚合材料已被用来提供较低的透湿性,以便减少通过包装膜的水份透过度,由此延长制品(例如食品、药品、电子产品、其他对湿度增加或减少敏感的物品)的贮存寿命。对于某些产品,希望保持高湿度,薄膜理论上缩小了湿度从包装到环境的损失;对于另一些制品,希望保持低湿度,薄膜理论上缩小了湿度从环境到包装材料中的增加。
通常还希望在包装薄膜中包含收缩特征,即:薄膜暴露于加热中收缩的倾向或者当限制时,在包装薄膜中产生收缩张力的倾向。这些性能通过在薄膜的制造过程中的薄膜取向而赋予它。通常所制的薄膜被加热至它的取向温度,在或者纵向(机器的)或者横向(即单轴取向)、或者双方向(即:双轴取向)以各种程度拉伸,以便给薄膜在后续的加热中赋予一定程度的收缩性。当进行双轴取向时,可同时或先后进行,即:可依次进行这些方向的每个方向的取向,或者纵向和横向取向两者同时进行。任何合适的技术(例如吹塑膜泡法、拉幅法)都可使用,以获得薄膜的取向。如此拉伸后,迅速冷却该薄膜,以便给所得的薄膜提供潜伏的收缩性。收缩薄膜的一个优点是如此所得的包装产品具有绷紧光滑的外观、提供了漂亮的包装以及防止了包装产品受环境的误用。各种食品和非食品物品可以并已经用收缩薄膜包装了。
有时还希望取向包装薄膜,然后通过将薄膜带到靠近它的取向温度,而热定形该薄膜。这产生了基本上很少收缩的薄膜,同时还保留了许多取向的优点,包括改进的拉伸强度,模量和光学性能。
本发明的一个目的是提供一种特征在于有好的防湿性能的热塑性塑料多层薄膜。
本发明的另一个目的是提供具有好的清晰度、漂亮的外观和其他所希望的光学性能的热塑性塑料多层薄膜。
本发明的再一个目的是提供具有韧性和耐磨性的、薄的热塑性塑料多层薄膜。
本发明的又一个目的是提供一种能完全共剂出、取向、并有好的防湿性、有时是既有防湿性又有阻氧性的热塑性塑料多层薄膜。
令人感兴趣的是描述了烃树脂应用的美国专利4,921,749(Bossaert等人的)、5,085,943(Crighton等人的);5,091,237(Schloegel等人的)、5,128,183(Buzio)和5,212,009(Peiffer等人的)。
本发明涉及一种热塑性塑料多层薄膜,该薄膜包含:一个芯层,该芯层包含丙烯聚合物或共聚物或者乙烯α-烯烃共聚物与烃树脂的掺混物;和两个外层,该外层包含丙烯聚合物或共聚物、乙烯α-烯烃共聚物,聚丁烯或它们的掺混物。
在另一方面,本发明涉及一种热塑性塑料多层薄膜,该薄膜包含:一个芯层,该芯层包含丙烯聚合物或共聚物与烃树脂的掺混物;两个中间层,该中间层位于芯层的相对侧面上,包含丙烯聚合物或共聚物或一个聚合粘合剂;和两个外层,该外层包含丙烯聚合物或共聚物,乙烯α-烯烃共聚物、高聚物、聚丁烯或它们的掺混物。
本发明还涉及一种热塑性塑料多层薄膜,包含一个芯层,该芯层包含乙烯α-烯烃共聚物、乙烯丙烯共聚物、橡胶改性乙烯丙烯共聚物或乙烯丙烯丁烯三元聚合物;两个中间层,该中间层位于芯层的相对侧面上,包含丙烯聚合物或共聚物与烃树脂的掺混物;和两个外层,该外层包含丙烯聚合物或共聚物、乙烯α-烯烃共聚物、离聚物、聚丁烯或它们的掺混物。
具有阻氧及防湿性能的薄膜包括:一个芯层,该芯层包含阻氧材料;两个中间层,该中间层位于芯层的相对侧面上,包含一个聚合粘合剂;两个外层,该外层包含丙烯聚合物或共聚物、或聚丁烯与烃树脂的掺混物;和一个粘合至外层至少之一上的聚合密封材料层。
具有至少七层的另一种薄膜包含:一个包含高密度聚乙烯的芯层;两个位于芯层的相对侧面上,包含一种聚合粘合剂、乙烯醋酸乙酯共聚物、或乙烯α-烯烃共聚物的中间层;两个包含丙烯聚合物或共聚物、聚丁烯或它们的掺混物的外层。
还有一种薄膜包括:一个包含一种阻氧材料的芯层;两个位于芯层的相对侧面上,包含聚酰胺的中间层;两个粘合层,其中每个设置在相应的聚酰胺层上,包含聚合粘合剂、乙烯α-烯烃共聚物、或乙烯醋酸乙酯共聚物;两个防湿层,其粘合到相应的粘合层上,包含丙烯聚合物或共聚物与烃树脂的掺混物,和两个包含丙烯聚合物、丙烯共聚物、乙烯α-烯烃共聚物或聚丁烯的最外层。
在本发明的另一方面,一种制造热塑性塑料多层薄膜的方法包括步骤如下:共挤出具有丙烯聚合物或共聚物与烃树脂掺混物的内层和包含丙烯聚合物或共聚物、乙烯α-烯烃共聚物、聚丁烯或它们的掺混物的两层外层,冷却共挤出的多层薄膜,并将冷却的薄膜夹扁。
在此所用的“烃树脂”(此文中为“HC”)意思是指由仅包含碳和氢的单体聚合得到的树脂,还包含由煤焦油馏份,汽油蒸馏物等衍生得到的较纯单体制得的低分子量热塑性树脂。对HC树脂的论述可见于例如美国专利4,921,749(Bossaert等人的),5,091,237(Schloegel等人的)和5,128,183(Buzio)中。
在此所用的“乙烯α-烯烃共聚物”(EAO)包含象线性低密度聚乙烯(LLDPE);非常低和超低密度聚乙烯(VLDPE和ULDPE);和金属茂催化的聚合物(例如由Exxon提供的那些)那样的材料。还包含由Mitsui提供的Tafmer(tm)材料。这些材料通常包含乙烯与一个或多个选自C4至C10α-烯烃(例如丁烯-1、己烯-1、辛烯-1等)共聚单体的共聚物,其中共聚物的分子包含具有较少侧支链或交联结构的长链。这种分子结构与普通的低或中密度聚乙烯相反,它们比它们的相应对应物被更高的支化。在此所定义的“LLDPE”的密度在每立方厘米约0.916g至每立方厘米0.940g的范围。通常,在此所用的“EAO”包含均聚物和非均相聚合物这两者。
在此所用的“中间层”定义为多层薄膜中由其他层在其两侧封住的层,即:设置在薄膜的其他层之间。
在此所用的词“取向的”定义了这样一种聚合材料,其中该分子通过例如拉幅或吹塑膜泡法在纵向和/或横向已被校直。
在此所用的“丙烯聚合物”是指以其均聚物形式的聚丙烯,而“丙烯共聚物”是指共聚物类,例如乙烯丙烯共聚物,在共聚物中通常包含少量的共聚单体(例如乙烯)。还可包括三元共聚物。
这里的“聚合粘合剂”是指聚合材料类(任何合适的组合物的),它可用于在多层热塑性塑料薄膜中产生或提高内层粘合力。聚烯烃是优选的,尤其是那样已改性的,例如由羧酸或酸酐改性成接枝共聚物的。
这里的“橡胶改性EPC”是指已经由聚合物结构中其它部分的包含物改性的EPC,这些材料可提供改进的弹性或其它性能。一个例子是Himont的KS-052P或以Rexene(E1 Paso)销售的那些。
在此所用的“乙烯丙烯丁烯三元共聚物”是指以各种百分比包含这三种组份的三元共聚物,一个例子是Himont的KT-021或由Sumitomo市售的那些。
这里所用的“芯层”是指多层薄膜的中间层和薄膜具有奇数层时的中心层。
下面将参考附图更详细地介绍。
附图简要说明:
图1是本发明多层防湿薄膜的优选实施例的示意横截面;
图2和图3是本发明另外的实施例。
尤其是参考附图,在图1中,显示了本发明多层防水薄膜一个优选实施例的示意横截面。多层薄膜10具有普通的A/B/A结构,其中A是外层,B是包括防湿材料的芯层。
芯层12优选包括丙烯聚合物或共聚物与烃树脂的掺混物,该掺混物被示作标点/标线层。丙烯均聚物的典型例子是Exxon PD 4067 E7或那些由Fina市售的或Himont的PD 064。优选的丙烯共聚物是以牌子Fina 8473或Fina 8437X销售的乙烯丙烯共聚物,该材料具有约4%的乙烯量。铖选的烃树脂是Regalrez 1128或1139(来自Hercules)。HC树脂优选占掺混物重量的约30%至50%之间。
外层14和16优选是乙烯丙烯共聚物(EPC),聚丙烯(PP)或它们的掺混物。如果仅仅使用聚丙烯树脂,则该薄膜用于包括热封的包装应用将是困难的。因此仅仅使用EPC或者两种材料的掺混物是优选的。市售树脂的例子是那些上述的用于芯层12的。用于外层14和16的其它聚丙烯是Himont PDO64。这个掺混物层包括从0-100%的EPC和100%-0%的PP,但优选该掺混物包括约96%至85%间的EPC和约4%至15%间的PP,甚至更优选,该掺混物层包括约92%的EPC和8%的PP。EAO和聚丁烯也可用于外层。
在图2中显示了本发明多层防湿薄膜的另一个实施例的示意性横截面图。多层薄膜具有A/B/C/B/A的结构,这里A是外层,B是中间粘合剂层,C是包含防湿材料的芯层。
该芯层优选包括丙烯聚合物或共聚物与烃树脂的掺混物。合适的材料是上述用于薄膜10的芯层12中的那些。
该外层优选是上述用于薄膜10的外层14和16中的那些材料,该外层还优选包括HC,例如所述用于薄膜10的芯层12的。
该中间层优选包含丙烯聚合物或共聚物或它们的掺混物,可选择性地与烃树脂掺混。
另一种A/B/C/B/A结构也在本发明范围之内,并通过图2薄膜的防湿层位置特别示出。
在这个另外方案中,芯层24优选包括一个乙烯α-烯烃共聚物,更优选是线性EAO。非常低密度聚乙烯(VLDPE)和线性低密度聚乙烯(LLDPE)是优选的。合适的LLDPE是Dowlex 2045。芯层24还可包括EPC、橡胶改性EPC或乙烯三元共聚物,尤其是乙烯丙烯丁烯三元共聚物,例如来自Himont的KT 021P。
外层20和28优选是上述用于薄膜10的外层14和16的材料。
中间层22和26优选包含丙烯聚合物或共聚物与烃树脂的掺混物,合适的材料是上述用于薄膜10芯层12的那些。层22和26的另一种材料是Exxon 6042,它是一种聚丙烯和烃树脂的掺混物。
在图3中,显示了本发明多层防湿薄膜的另一实施例的示意横截面。多层薄膜30具有普通的A/B/C/D/C/B/A结构,其中A是外层,B是防湿层,C是中间粘合层,D是包含阻氧材料的芯层。
芯层38优选包含阻氧材料,例如乙烯乙烯醇共聚物、偏二氯乙烯共聚物、聚酯或聚酰胺。
外层32和44优选是上述薄膜10的外层14和16的材料。
中间层36和40优选包含丙烯聚合物或共聚物,例如Exxon PD 4062 E7。另一种材料是聚合粘合剂,特别是羧酸或马来酸酐改性的聚烯烃,特别是聚丙烯基羧酸或马来酸酐改性的粘合剂。普通的复合或其他合适的方法有时是必须的,这取决于各层的特性,以确保足够的层间连接强度。
防湿层34和42优选包含丙烯聚合物或共聚物与烃树脂的掺混物,合适的材料是上述用于薄膜10的芯层12的那些。用于层34和42的另一种材料是Exxon 6042。
具有至少七层的另一种薄膜包括一个芯层38(包含高密度聚乙烯);两个中间层36和40(在芯层的各相对侧面上,包含聚合粘合剂,乙烯醋酸乙酯共聚物或乙烯α-烯烃共聚物),两个防湿层34和42(包含丙烯聚合物或共聚物与烃树脂的掺混物),两个最外层32和44(包含丙烯聚合物或共聚物)。
根据本发明,四层或六层和、或既具有防湿也具有阻氧性能的多层薄膜也是可以制造的。在这种另外结构中,HC树脂与丙烯聚合物或共聚物的掺混物可存在于该多层薄膜各层的任一之中。
这种薄膜的芯层、中间层和防湿层可与薄膜30的相同。一个密封材料层可用现有技术已知的手段和方法共挤或挤出涂复,挤出复合或粘接复合到防湿层之一上。设置在薄膜结构的一或两外侧面上的密封材料层优选包含乙烯α-烯烃共聚物,尤其是线性EAO,而非常低密度聚乙烯(VLDPE)和线性低密度聚乙烯(LLDPE)是优选的。合适的LLDPE是Dowlex 2045。密封材料层还可包含EPC、橡胶改性EPC、乙烯丙烯丁烯三元共聚物(例如Himont的KT 021P)、乙烯醋酸乙酯共聚物、乙烯丙烯酸烷基酯共聚物、乙烯丙烯酸或甲基丙烯酸共聚物或离聚物。
本发明的薄膜可通过共挤、挤出涂复、挤出复合和普通的粘合复合这些现有技术已知的技术,使用合适的环状或平缝模头挤出设备制造。
好的低湿度穿透率(高防湿)和其它与本发明典型薄膜相关的性能被表示在下面的表中。
这些例子所用的树脂被标记在表1中,由这些树脂制造的薄膜标记在表2至8中。
这些薄膜的物理性能则分别列于其余的表中。给出的值一般是由四个重复测量得到的平均值,用于MVTR的值是从三个试样得到的平均值。
在表中的项目和缩写具有下列的含义:
“PP”=聚丙烯。
“EPC”=乙烯丙烯共聚物。
“EAO”=乙烯α-烯烃共聚物。
“EPB”=乙烯丙烯丁烯三元共聚物。
“EVOH”=乙烯乙烯醇共聚物。
“ADH”=聚合粘合剂;ADH1是来自Du Pont的乙烯丁烯基粘合剂,ADH 2是来自Mitsui的EPC-基粘合剂。
“AB”=抗粘连。
“MO”=矿物油。
“拉伸”=73°F(22.8℃)断裂时的拉伸,单位PSI(ASTM D 882-81)。
“PSI”=每平方英寸磅(ASTM882-81)。
“不收缩”=对于所述的性能在试验的时间下通过暴露于加热中不收缩的薄膜试样。
“收缩”=对于所述的性能在试验的时间下通过暴露于加热中收缩的薄膜试样。
“LD”=纵拉伸方向。
“TD”=横拉伸方向。
“模量”=在73°F时的弹性模量(ASTM882-81)单位:PSI
“雾度”=雾度(ASTM D 1003-61(1977年重新批准的))单位:%。
“清晰度”=所有光的透射率(ASTM D 1003 方法A)单位:%。
“光泽”=相对于薄膜表面45°角测量的光泽(ASTM D 2457-70(1977年重新批准的))。
“MVTR 1”=湿(水)蒸汽透过率(ASTMF 372)单位:g/24h 100英寸2(645cm2(在100%相对湿度和100°F(37.8℃))。
“MVTR 2”=湿(水)蒸汽透过率(ASTM F 372)单位:g/24h 100英寸2(在90%相对湿度和100°F)。
“OTR”=氧透过率(ASTM D 3985-81)单位cm3(标准湿度和压力下的)/24h/m2(在1个大气压下,在0%相对湿度)。
“撕裂”=撕裂增生,在73°F(ASTM D 1938-79)单位:克。
“薄膜厚度”=薄膜试样的平均厚度(gauge),单位:密耳(=2.54×10-2mm)。
“拉伸”=断裂时的拉伸强度(ASTM D 882-81)单位:psi。
“伸长”=断裂时的伸长(ASTM D 882-81)单位:%。
“球破裂”=球破裂冲击,单位厘米-千克,在73°F(ASTM D 3420-80)。
表1
材料 商标 供应商
PP 1 Profax PD-064 Himont
PP 2* (见脚注)
PP 3 PD 4062 Exxon
PP 4** Escorene PD 6042 Exxon
(见脚注)
EPC 1 Fina 8473 或 Fina
Fina 8473 X
EPC 2*** (见脚注)
EPC 3 PD 9302 Exxon
EPB 1 KT-021 Himont
HC 1 Regalrez 1128 Hercules
HC 2 Escorez 5340 Exxon
HC 3 Regalrez 1139 Hercules
EAO 1 Dowlex 2045.03 Dow
EAO 2 Dowlex 2045.04 Dow
ADH 1 Bynel CXA 4104 Du Pont
ADH 2 Admer QF 551 A Mitsui
EVOH 1 EVAL SC H-103 Evalca
EVOH 2 EVAL LC F-101 A Evalca
EVOH 3 EVAL LC H-103 Evalca
MO 1 Kaydol Witco
续表1
*PP2是PP1与约4%掺混物重量的含硅抗粘连剂,约5%重量的酰胺蜡和约1%的润滑剂的母料掺混物。酰胺蜡和润滑剂在现有技术中作为滑爽剂(slip agents)是已知的。
**PP4是Escorene PD 6042,
它是聚丙烯和烃树脂的掺混物。
***EPC2是EPC1与约1.5%掺混物重量的
抗粘连剂和0.5%掺混物重量的矿物油掺混的掺混物。
表2(对比)
最初的制造防湿材料的努力包括在芯层使用聚丙烯均聚物,而在芯层两侧面具有含丙烯共聚物的密封层,目的是增大芯层的厚度,减少湿汽透过速率(MVTR),同时仍保持足够的薄膜密封性能和自由收缩性能。对于至少某些防湿包装应用该MTVR不能证明是足够的。
该薄膜的例子给出如下:
例 薄膜结构
1、92% EPC1+8% PP2/PP1/
92% EPC1+8% PP2
例1的薄膜一般结构是A/B/A。
相对层厚比:A=1.0;B=2.0;A=1.0。
表3
表3的薄膜是为了努力制造具有低MVTR的防湿材料而制的。通过使用与聚丙烯均匀物掺混的烃树脂达到了,并发现该配方比表2的具有更低的湿汽透过率(MVTR)。但由于装置限制,它们不能取向大于4.5×4.5变形(取向)比。在其它装置上(例如改进的膜泡工艺或拉幅法),可以达到较高的取向(变形)比。由于相对较差的撕裂性能,它们还不能制成大厚度薄膜。该薄膜的例子如下:
例 薄膜结构
2、90%[92% EPC 1+8% PP 2]+10% HC 1/
PP 3/
84.5% PP3+15% HC 1+0.5% MO 1/
PP 3/
90%[92% EPC 1+8% PP 2]+10% HC 1
例2薄膜的一般结构是A/B/C/B/A。
相对层厚比:2.5:0.8:3.7:0.6:2.4。
3、92% EPC 1+8% PP 2/
PP4/
92% EPC 1+8% PP 2
例3薄膜的一般结构是A/B/A。
相对层厚比:1:2:1。
4、92% EPC 1+8% PP 2/
续表3
PP 4/
92% EPC 1+8% PP 2
例4薄膜的一般结构是A/B/A。
相对层厚比:1:3:1。
表4
制造表4的各类薄膜,其中事实上表3薄膜的芯层(即含有烃树脂的层)被"合成"两个基片(中间)层)
,一个"新"的芯层(例如LLDPE或EPC的)被插入。这样的实际效果改进了在取向过程中的相对于带折缝的薄膜的撕裂性能,因此它能以例如6×6的比例取向。实际上由于装置的限制(如表3中的例子所述的),该薄膜以4×4.5取向。该薄膜的例子如下:
例 薄膜结构
5、92% EPC 1+8% PP 2/PP 4/
EAO 1/PP 4/92% EPC 1+8% PP 2
例5的薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
6、92% EPC 1+8% PP 2/PP 4/EPC 1/PP 4/
92% EPC 1+8%PP 2
例6薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5
表5
本发明人取表4的基本结构,并将它们以高的变形比6×6取向,结果薄膜显示出改进的(即:低的)MVTR。这些薄膜的实施例如下:
例 薄膜结构
7、92% EPC 1+8% PP 2/PP 4/EAO 1/PP 4/
92% EPC 1+8% PP 2
例7薄膜的一般结构是A/B/C/B/A,该薄膜与
例5的相同,但分别在纵向和横向具有MD和TD变形比为约6×6。
相对层厚比:1.5:3:1:1.5
8、92% EPC 1+8% PP 2/PP 4/EAO 1/PP 4/
92% EPC 1+8% PP 2
例8薄膜的一般结构是A/B/C/B/A,该薄膜与
例7的相同,但在比例7更高的温度下取向。
相对层原比:1.5:3:1:3:1.5
9 92% EPC 1+8% PP 2/PP 4/EAO 2/PP 4/
92% EPC 1+8% PP 2
例9薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
10.92% EPC 1+8% PP 2/PP 4/EPB 1/PP 4/
92% EPC 1+8% PP 2
续表5
例10薄膜的一般结构为A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
11、92% EPC 1+8% PP 2/
70% PP 3+30% HC 2/
EAO 2/
70% PP3+30% HC2/
92% EPC 1+8% PP 2
例11薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
12、90% EPC 1+10% PP 2/PP 4/EPC 1/PP 4/
90% EPC 1+10% PP 2
例12'的薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
13、90% EPC 1+10% PP 2/PP 4/EPC 1/PP 4/
90% EPC 1+10% PP 2
例13薄膜的一般结构是A/B/C/B/A。该薄膜与例12的相同,但变形比较低为4.5×4.5,以生产132厚度的薄膜。
相对层厚比:1.5:3:1:3:1.5
14、90% EPC 1+10% PP 2/PP 4/EPC 1/PP 4/
90% EPC 1+10% PP 2
例14薄膜的一般结构是A/B/C/B/A,该薄膜
与例13的相同,但具有稍高的变形比(4.5×
5.0),最终的薄膜厚度为155。
续表5
相对层厚比:1.5:3:1:3:1.5
15、87.5% EPC 3+12.5% PP 2/PP 4/EPC 3/PP 4/
87.5% EPC 3+12.5% PP 2
例15薄膜的一般结构是A/B/C/B/A,
相对层厚比:1.5:3:1:3:1.5
16、84% EPC 3+16% PP 2/PP 4/EPC 3/PP 4/
84% EPC 3+16% PP 2
例16薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
17、86% EPC 3+14% PP 2/PP 4/EPC 3/PP 4/
86% EPC 3+14% PP 2
例17薄膜的一般结构是A/B/C/B/A。
相对层厚比:1.5:3:1:3:1.5。
表6
本发明人制出了一个七层薄膜(例18)作为对比,然后制出了两个防湿/阻氧七层薄膜(例19和例20),具有好的结果。这些薄膜的例如下:
例 薄膜结构
18、92% EPC 1+8% PP 2/PP 3/ADH 2/EVOH 1/
ADH 2/PP 3/92% EPC 1+8% PP2
例18薄膜的一般结构是A/B/C/D/C/B/A。
相对层厚比:1:2.5:1:1:1:2.5:1。
续表6
19、92% EPC 1+8% PP 2/PP 4/ADH 1/EVOH 2/
ADH 1/PP 4/ 92% EPC 1+8% PP 2
例19薄膜的一般结构是A/B/C/D/C/B/A。
相对层厚比:1.5:2:1:1:1:2:1.5。
20、92% EPC 1+8% PP 2/PP 4/ADH 2/
EVOH 3/ADH 2/PP 4/ 92% EPC 1+8% PP 2
例20薄膜的一般结构是A/B/C/D/C/B/A。
相对层厚比:1.5:2:1:1:1:2:1.5。
表7
两种另外的七层薄膜的结构为:
21、92% EPC 1+8% PP 2/PP 4/EVA 1/HDPE 1/
EVA 1/PP 4/92% EPC 1+8% PP 2
例21薄膜的一般结构是A/B/C/D/C/B/A。
相对层厚比:1:2.5:1:1:1:2.5:1。
22、92% EPC 1+8% PP 2/PP 4/VLDPE 1/
HDPE 1/VLDPE 1/PP 4/ 92% EPC 1+8% PP 2
例22薄膜的一般结构是A/B/C/D/C/B/A。
相对层厚比:1:2.5:1:1:1:2.5:1。
表8
制出两种另外的五层薄膜,并在表13中与例17的薄膜比较。这两种另外的薄膜具有下面的结构。
23、86% EPC 3+14% PP 2/PP 4/85 EPC 3+15%
HC 3/PP 4/86% EPC 3+14% PP 2
例23的薄膜的一般结构为:A/B/C/B/A
相对层厚比:1.5:3:1:3:1.5
24、86%[85% EPC 3+15% HC 3]+14% PP 2/PP 4
85% EPC 3+15% HC 3/PP 4/85% EPC 3+
15% HC 3
例24薄膜的一般结构为:A/B/C/B/C
相对层厚比:1.5:3:1:3:1.5
表9
例1 例2 例3 例4
(对比)
模量
Ld 239,480 279,920 316,030 336,820
Td 214,690 260,240 298,930 316,820
自由收缩/收缩张力
在200°F(93.3℃)
LD 7/396 9/321 10/315 11/408
TD 12/388 14/381 17/528 17/504
在220°F(104.4℃)
续表9
LD 12/435 14/335 14/361 15/439
TD 18/432 19/383 24/540 25/548
在240°F(115.6℃)
LD 18/451 20/364 20/443 22/494
TD 26/469 28/413 33/591 33/516
在260°F(126.7℃)
LD 31/473 31/397 33/429 33/511
TD 35/493 39/441 45/538 44/561
雾度
未收缩 1.2 1.7 1.3 1.3
收缩 1.6 2.3 3.2 2.1
清晰度
未收缩 81 87 87 88
收缩 80 84 83 80
光泽
87 84 87 88
薄膜厚度(密耳)
(相对于给出如下的MVTR数据)
未收缩
实际的 0.96 0.80 0.77 0.75
MVTR 1
未收缩
0.60 0.67 0.60 0.55
对75厚度校正的
0.77 0.71 0.62 0.55
MVTR 2
续表9
未收缩
0.49 0.55 0.48 0.45
对75厚度校正的
0.63 0.59 0.49 0.45
表10
例7 例8 例9 例10
模量
LD 271,200 299,200 ------ ------
TD 292,100 337,900 ------ ------
自由收缩
在220°F
LD -- -- 13 13
TD -- -- 19 20
在240°F
LD 20 17 20 18
TD 28 23 30 27
在260°F
LD -- -- 27 28
TD -- -- 37 38
雾度
未收缩
-- -- 1.7 1.8
清晰度
未收缩
-- -- 82 84
光泽
-- -- 84 85
薄膜厚度(密耳)
(相对于给出如下的MVTR数据)
未收缩
续表10
0.86 0.76 0.86 0.77
收缩
1.00 0.97 ---- ----
MVTR 1
未收缩
0.51 0.56 ---- ----
收缩
0.41 0.46 ---- ----
对75厚度校正的
未收缩
0.58 0.57 ---- ----
收缩
0.55 0.59 ---- ----
MVTR 2
未收缩
0.45 0.47 0.42 0.43
收缩
0.35 0.38 ---- ----
对75厚度校正的
未收缩
0.52 0.48 0.48 0.44
收缩
0.47 0.49 ---- ----
撕裂(克)
LD -- -- 8.6 5.0
TD -- -- 8.4 6.1
表11
例11 例12 例13 例14
模量
LD 345,750 352,880 322,950 320,470
TD 374,990 392,020 334,660 319,420
自由收缩
在240°F
LD 20 17 18 14
TD 29 23 24 25
雾度
未收缩
48.5 1.3 3.3 5.3
清晰度
未收缩
21 85 74 64
光泽
107 89 73 64
薄膜厚度(密耳)
(相对于给出如下的MVTR数据)
未收缩
0.85 0.81 1.40 1.60
MVTR 2
未收缩
0.36 0.36 0.23 0.19
对75厚度校正的
0.41 0.39 0.43 0.41
撕裂(克)
LD -- -- 8.6 5.0
TD -- -- 8.4 6.1
表12
例19 例20
LD 300,890 307,380
TD 315,460 291,480
自由收缩/收缩张力
在220°F:
LD 8/440 14/395
TD 19/632 20/595
在240°F:
LD 18/477 21/439
TD 28/654 27/611
在260°F:
LD 28/446 29/436
TD 38/621 35/601
在280°F:
LD 44/467 43/487
TD 52/600 46/587
在300°F:
LD 59/--- 60/---
TD 62/--- 61/---
雾度
未收缩 1.6 1.8
续表12
透明度
未收缩 76 76
光泽
89 86
薄膜厚度(密耳)
(相对于如下给出的MVTR数据)
未收缩 1.09 1.12
MVTR2
未收缩
0.35 0.33
对75厚度校正的
0.51 0.49
撕裂
LD 6 6
TD 6 7
拉伸
LD 19,415 202,407
TD 19,296 16,990
伸长
LD 63 62
TD 71 77
球破裂
12 11
OTR
3.0 4.5
表13
例17 例23 例24
模量
LD 398,000 420,000 437,000
TD 442,000 473,000 488,000
自由收缩
在220°F:
LD 15 14 15
TD 19 19 22
在240°F:
LD 20 19 19
TD 26 26 28
在260°F:
LD 30 30 26
TD 38 36 38
在280°F:
LD 44 44 44
TD 51 51 52
在300°F:
LD 64 63 62
TD 68 67 68
雾度
续表13
未收缩 1.8 2.0 1.2
透明度
未收缩
82 81 81
光泽
86 83 89
薄膜厚度密耳
(相对于如下给出的MVTR数据)
未收缩
0.89 0.91 0.82
MVTR 2
未收缩
0.33 0.36 0.33
对75厚度校正的
0.39 0.44 0.36
撕裂
LD 1 7 4
TD 5 7 6
拉伸
LD 28,000 31,000 28,000
TD 29,000 33,000 29,000
伸长
LD 80 86 84
TD 71 52 73
在一个制造本发明薄膜的曲型加工例子中:
含有约4%重量乙烯的乙烯丙烯共聚物(Fina8473)与聚丙烯以约92%重量的EPC和8%重量的PP的掺混比例掺混。(该面分比包含上述的添加剂)。
该EPC/PP掺混物然后与烃树脂(来自Hercules的Regalrez 1128)以约90%重量的EPC/PP和10%重量的HC的掺混比掺混。
以约84.5%重量PP(Exxon PD 4062E7),15%重量HC(Regalrez 1128)和0.5%重量白色矿物油(来自Witco Chemical的Kaydol)的掺混比,制备第二种掺混物。
用三台挤出机给环形共挤压模头供料,以制备五层收缩膜。使用一台挤压机供应EPC或聚丙烯与HC的掺混物作为熔体到挤出模头,以形成外层,另一台挤出机供应聚丙烯(Exxon PD 4062 E7)至挤出模头,以提供多层薄膜的中间层,第三台挤出机提供PD和HC的第二种掺混物到挤出机头。
挤出的带状物迅速冷却至室温,并用夹膜辊夹膜。该带状物接着加热至取向温度,使用现有技术已知的膜泡技术,以内空气压力在纵(机器)向拉伸该带状物至其未拉伸尺寸的4.5位,并在横向拉伸至其未拉伸尺寸的4.0倍,以形成一个膜泡,该膜泡在所形成的薄膜上提供了双轴取向。通过冷却空气迅速冷却该膜泡,以便保持薄膜的取向状态。最后,该膜泡被夹扁,该拉伸的薄膜收卷在卷取辊上。取向后,该薄膜的总壁厚约1密耳,结构的50%是乙烯丙烯共聚物和聚丙烯的掺混物,结构的15%是中间层,结构的其余部分或35%是芯层。
本领域的普通技术人员非常清楚,根据包装应用,可改变拉伸的程度,以得到所希望程度的薄膜厚度,并调整所希望量的收缩张力、自由收缩和最终薄膜的其它收缩性能。优选的拉伸或变形比是在约3.0至8.0之间(在机器方向及横向上)。
本发明的多层薄膜优选是不辐照的。但是,密封材料(如果挤出复合、挤出涂复或普遍的复合到基材防湿薄膜上)本身在复合之前可被辐射或电或化学交联。辐照可由现有技术已知的方式完成。
EPC和PP的掺混比可根据多层薄膜的所希望性能和最后应用改变。例如在掺混中增加聚丙烯将给薄膜增加韧性但也增加薄膜的封合温度。相反,在掺混物中增加EPC趋向于降低取向薄膜的收缩温度或增加同一温度的收缩,还降低了薄膜的封合温度。优选的掺混物包含约4%至15%的PP及约96%和85%间的EPC。
本发明的多层薄膜优选是或者单轴或者双轴取向的,并且优选用作收缩薄膜。可以选择地,该取向薄膜可通过再加热薄膜至接近它的取向温度(即:或者略低、或者在、或者大约在它的取向温度)而进一步加工,以热定形该薄膜。该进一步加工步骤具有基本上保留了许多取向薄膜令人希望的物理性能(例如高拉伸强度,模量和改进的光学性能)同时提供给不希望收缩特征的应用场合基本上不收缩的薄膜的优点。
本发明的薄膜可在该薄膜的至少一个或多个或甚至全部层中使用烃树脂,只要在任何给定的层中的HC树脂以加工和性能的观点看与和它相掺混的树脂相容就行。
根据本发明的薄膜优选是取向的,并优选是可热收缩的。优选的薄膜在240°F显示出至少10%(LD)和15%(TD),更优选至少15%(LD)和22%(TD)的自由收缩。
本领域的普通技术人员不脱离本发明的权利要求的精神和范围可以做出正如所述的对本发明的明显改进。
Claims (19)
1、一种热塑性塑料多层薄膜,包含:
(a)一个芯层,包含丙烯聚合物或共聚物与烃树脂的掺混物,和
(b)两个外层,包含一选自如下的聚合材料;
ⅰ)丙烯聚合物,
ⅱ)丙烯共聚物,
ⅲ)乙烯α-烃共聚物,
ⅳ)聚丁烯,和
ⅴ)它们的掺混物。
2、根据权利要求1的薄膜,其中聚丙烯占外层重量的约4至15%。
3、根据权利要求1的薄膜,其中芯层重量的1%至50%包含烃树脂。
4、根据权利要求1的薄膜,其中芯层重量的20%至40%包含烃树脂。
5、根据权利要求1的薄膜,其中薄膜是双轴向拉伸的。
6、根据权利要求5的薄膜,其中该薄膜在纵向和横向双方向以3∶1至8∶1的比例拉伸而取向。
7、根据权利要求1的薄膜,其中外层的丙烯共聚物包含2%至5%重量的乙烯共聚单体。
8、一种热塑性塑料多层薄膜,包含:
(a)一个芯层,包含丙烯聚合物或共聚物与烃树脂的掺混物;
(b)两个位于芯层相对侧面的中间层,包含丙烯聚合物或共聚物或聚合的粘合剂;及
(c)两个外层,包含选自如下的聚合材料:
ⅰ)丙烯聚合物,
ⅱ)丙烯共聚物,
ⅲ)乙烯α-烯烃共聚物,
ⅳ)离聚物,
ⅴ)聚丁烯,和
ⅵ)它们的混合物。
9、根据权利要求8的薄膜,其中聚合粘合剂是聚烯烃基羧酸或马来酸酐改性的粘合剂。
10、一种热塑性塑料多层薄膜,包含:
(a)一个芯层,包含一个选自如下的材料:
ⅰ)乙烯α-烯烃共聚物,
ⅱ)乙烯丙烯共聚物,
ⅲ)橡胶改性EPC,和
ⅳ)乙烯丙烯丁烯三元共聚物;
(b)两个位于芯层相对侧面上的中间层,包含丙烯聚合物或共聚物与烃树脂的掺混物;和
(c)两个外层,包含选自如下的聚合材料:
ⅰ)丙烯聚合物,
ⅱ)丙烯共聚物,
ⅲ)乙烯α-烯烃共聚物,
ⅳ)离聚物,
ⅴ)聚丁烯,和
ⅵ)它们的掺混物。
11、一种热塑性塑料多层薄膜,包含:
a)一个芯层,包含一种阻氧材料,
b)两个位于该芯层的相对侧面上的中间层,包含一聚合粘合剂;
c)两个外层,包含丙烯聚合物或共聚物与烃树脂的掺混物;和
d)一个粘合到至少外层之一上的聚合密封材料层。
12、根据权利要求11的薄膜,其中阻氧层包含选自如下的聚合材料:
ⅰ)乙烯乙烯醇共聚物,
ⅱ)偏二氯乙烯共聚物,
ⅲ)聚酯,和
ⅳ)聚酰胺。
13、根据权利要求11的薄膜,其中密封材料层包含选自如下的聚合材料:
ⅰ)丙烯聚合物,
ⅱ)丙烯共聚物,
ⅲ)乙烯α-烯烃共聚物,
ⅳ)离聚物
ⅴ)聚丁烯,和
ⅵ)它们的掺混物。
14、一种热塑性塑料多层薄膜,包含:
a)一个芯层,包含高密度聚乙烯;
b)两个位于该芯层相对侧面上的中间层,包含选自如下的聚合材料:
ⅰ)聚合粘合剂;
ⅱ)乙烯醋酸乙酯共聚物;和
ⅲ)乙烯α-烯烃共聚物;
c)两个外层,包含丙烯聚合物或共聚物与烃树脂的掺混物;和
d)两个最外层,包含丙烯聚合物或共聚物、聚丁烯或它们的掺混物。
15、一种热塑性塑料多层薄膜,包含:
(a)一个芯层,包含阻氧材料;
(b)两个位于芯层相对侧面上的中间层,包含聚酰胺;
(c)两个设置在相应聚酰胺层上的粘合层,包含选自如下的聚合材料:
ⅰ)聚合粘合剂;
ⅱ)乙烯α-烯烃共聚物;和
ⅲ)乙烯醋酸乙酯共聚物;
(d)两个粘合到相应粘合剂层上的防湿层,包含丙烯聚合物或共聚物与烃树脂的掺混物;和
e)两个最外层,包含选自如下的聚合材料:
ⅰ)丙烯聚合物,
ⅱ)丙烯共聚物,
ⅲ)乙烯α-烯烃共聚物,和
ⅳ)聚丁烯。
16、一种制造共挤出多层薄膜的方法,包括以下步骤:
a)共挤出一层包含丙烯聚合物或共聚物与烃树脂的掺混物的内层及两层包含丙烯聚合物,丙烯共聚物、乙烯α-烯烃共聚物、离聚物、聚丁烯或它们的掺混物外层;
(b)冷却共挤出的多层薄膜;和
(c)夹扁冷却的薄膜。
17、根据权利要求16的方法,该方法进一步包含再加热所述的夹扁薄膜、并拉伸和取向该加热薄膜的步骤。
18、根据权利要求17的方法,其中加热的带状物在纵和横向两个方向以3∶1至8∶1的比例拉伸。
19、根据权利要求17的方法,该方法进一步包含将取向薄膜再加热至接近它的取向温度的步骤。
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US94724492A | 1992-09-18 | 1992-09-18 | |
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CN1084452A true CN1084452A (zh) | 1994-03-30 |
CN1067017C CN1067017C (zh) | 2001-06-13 |
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US (3) | US5543223A (zh) |
EP (1) | EP0588667A2 (zh) |
JP (1) | JP3342127B2 (zh) |
CN (1) | CN1067017C (zh) |
AU (2) | AU674873B2 (zh) |
BR (1) | BR9303823A (zh) |
CA (1) | CA2106258C (zh) |
MX (1) | MX9305734A (zh) |
NZ (1) | NZ248674A (zh) |
PH (1) | PH31580A (zh) |
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DE3921358A1 (de) * | 1989-06-29 | 1991-01-10 | Hoechst Ag | Biaxial orientierte polypropylenfolie mit hoher mechanischer festigkeit |
JPH0645226B2 (ja) * | 1989-08-29 | 1994-06-15 | チッソ株式会社 | 不透明積層延伸成形物およびその製造方法 |
DE3940173A1 (de) | 1989-12-05 | 1991-06-06 | Hoechst Ag | Beidseitig siegelbare, biaxial orientierte polyolefin-mehrschichtfolie, ihre herstellung und ihre verwendung |
ES2071039T3 (es) * | 1990-02-01 | 1995-06-16 | Borden Inc | Pelicula modificada de poliolefina con retencion estable del arrollamiento, propiedades de plegado completo y caracteristicas de barrera. |
US5128183A (en) * | 1990-08-01 | 1992-07-07 | Borden, Inc. | Modified polyolefin film with stable twist retention, dead fold properties and barrier characteristics |
GB9010092D0 (en) * | 1990-05-04 | 1990-06-27 | Ici Plc | Polyolefin film |
US5204182A (en) * | 1990-05-04 | 1993-04-20 | Imperial Chemical Industries Plc | Polyolefin film |
NZ237981A (en) * | 1990-05-17 | 1993-12-23 | Grace W R & Co | Multilayer polymeric film having a polyamide core; high |
NZ237840A (en) * | 1990-05-25 | 1993-05-26 | Grace W R & Co | High density polyethylene shrink film |
JPH0477235A (ja) * | 1990-07-18 | 1992-03-11 | Honshu Paper Co Ltd | 熱収縮性ポリプロピレンフィルム |
US5429862A (en) | 1990-07-21 | 1995-07-04 | Hoechst Aktiengesellschaft | Biaxially oriented sealable polypropylene film having improved barrier properties |
DE4030385A1 (de) * | 1990-09-26 | 1992-04-02 | Hoechst Ag | Transparente schrumpffolie aus biaxial orientiertem polypropylen fuer die rundumetikettierung |
US5110677A (en) * | 1990-10-01 | 1992-05-05 | W. R. Grace & Co.-Conn. | Lettuce packaging film |
DE4037417A1 (de) * | 1990-11-24 | 1992-05-27 | Hoechst Ag | Metallisierbare dreheinschlagfolie aus biaxial orientiertem polypropylen |
DE4038935A1 (de) * | 1990-12-06 | 1992-06-11 | Hoechst Ag | Beidseitig siegelbare, biaxial orientierte polyolefinmehrschichtfolie mit erhoehtem schrumpf und verbesserten barriereeigenschaften |
IT1246769B (it) * | 1990-12-24 | 1994-11-26 | Polifilms Srl | Films multistrato termoretraibili perfezionati a base di resine olefiniche contenenti anche resine non olefiniche. |
US5152946A (en) * | 1991-01-30 | 1992-10-06 | Hercules Incorporated | Producing low shrink packaging film |
JP3104885B2 (ja) * | 1992-03-13 | 2000-10-30 | 大倉工業株式会社 | 熱収縮性積層フィルム |
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-
1993
- 1993-09-15 CA CA 2106258 patent/CA2106258C/en not_active Expired - Fee Related
- 1993-09-15 NZ NZ248674A patent/NZ248674A/en not_active IP Right Cessation
- 1993-09-16 PH PH46883A patent/PH31580A/en unknown
- 1993-09-16 AU AU47378/93A patent/AU674873B2/en not_active Ceased
- 1993-09-17 BR BR9303823A patent/BR9303823A/pt not_active IP Right Cessation
- 1993-09-18 CN CN93117538A patent/CN1067017C/zh not_active Expired - Fee Related
- 1993-09-20 JP JP25651993A patent/JP3342127B2/ja not_active Expired - Fee Related
- 1993-09-20 MX MX9305734A patent/MX9305734A/es unknown
- 1993-09-20 EP EP19930307403 patent/EP0588667A2/en not_active Withdrawn
-
1994
- 1994-12-16 US US08/358,121 patent/US5543223A/en not_active Expired - Fee Related
-
1995
- 1995-04-28 US US08/431,225 patent/US5910374A/en not_active Expired - Lifetime
- 1995-04-28 US US08/430,632 patent/US6579621B1/en not_active Expired - Fee Related
-
1996
- 1996-10-25 AU AU70537/96A patent/AU695543B2/en not_active Ceased
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100429073C (zh) * | 2003-03-31 | 2008-10-29 | 东赛璐株式会社 | 阻透性层积膜及其制造方法 |
CN100448667C (zh) * | 2003-04-03 | 2009-01-07 | 普瑞曼聚合物株式会社 | 包装用膜 |
CN101585254A (zh) * | 2008-05-19 | 2009-11-25 | 霍尼韦尔国际公司 | 采用功能性聚合物涂层来改进当前的可再生膜的性能 |
CN101585254B (zh) * | 2008-05-19 | 2015-03-25 | 霍尼韦尔国际公司 | 采用功能性聚合物涂层来改进当前的可再生膜的性能 |
CN102666286A (zh) * | 2009-11-13 | 2012-09-12 | 应用材料公司 | 具有增强寿命的部件 |
CN102666286B (zh) * | 2009-11-13 | 2014-11-26 | 应用材料公司 | 具有增强寿命的部件 |
TWI686301B (zh) * | 2015-07-24 | 2020-03-01 | 日商迪愛生股份有限公司 | 積層薄膜及包裝材料 |
CN113302063A (zh) * | 2018-12-27 | 2021-08-24 | 美国圣戈班性能塑料公司 | 打印机组件低摩擦辊衬垫 |
CN113302063B (zh) * | 2018-12-27 | 2023-03-10 | 美国圣戈班性能塑料公司 | 打印机组件低摩擦辊衬垫 |
US11708857B2 (en) | 2018-12-27 | 2023-07-25 | Saint-Gobain Performance Plastics Corporation | Solenoid low friction bearing liner |
CN114229246A (zh) * | 2021-12-21 | 2022-03-25 | 石家庄育才药用包装材料股份有限公司 | 缓冲液用集装袋 |
Also Published As
Publication number | Publication date |
---|---|
JPH06198826A (ja) | 1994-07-19 |
US5910374A (en) | 1999-06-08 |
MX9305734A (es) | 1994-06-30 |
NZ248674A (en) | 1996-03-26 |
EP0588667A2 (en) | 1994-03-23 |
CA2106258A1 (en) | 1994-03-19 |
EP0588667A3 (zh) | 1994-08-03 |
AU4737893A (en) | 1994-03-24 |
US5543223A (en) | 1996-08-06 |
CA2106258C (en) | 2003-11-04 |
CN1067017C (zh) | 2001-06-13 |
AU674873B2 (en) | 1997-01-16 |
JP3342127B2 (ja) | 2002-11-05 |
US6579621B1 (en) | 2003-06-17 |
AU695543B2 (en) | 1998-08-13 |
PH31580A (en) | 1998-11-03 |
AU7053796A (en) | 1997-01-16 |
BR9303823A (pt) | 1994-03-22 |
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