CN1032424A - 不等同双轴取向的高密度聚乙烯膜 - Google Patents

不等同双轴取向的高密度聚乙烯膜 Download PDF

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CN1032424A
CN1032424A CN88106971A CN88106971A CN1032424A CN 1032424 A CN1032424 A CN 1032424A CN 88106971 A CN88106971 A CN 88106971A CN 88106971 A CN88106971 A CN 88106971A CN 1032424 A CN1032424 A CN 1032424A
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hdpe
weight
melt index
density polyethylene
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CN1014899B (zh
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陆邦嘉
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Incomparable Oil Co
ExxonMobil Oil Corp
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

取向为在机器方向变形比约为2而在横向变形 比约为6或大于6的高密度聚乙烯膜，最好是含有高 密度聚乙烯树脂或微晶蜡，这类膜具有好的死折性和 水汽透过性，当它们涂以一种可热封层，如一种离聚 物或与这离聚物共挤出时使这类膜非常适于包装，特 别是用于干食物的包装。

Description

把含有乙烯-醋酸乙烯酯可热封涂层的高密度聚乙烯吹塑膜用于食品包装。然而这样的膜必须有大约2密尔厚以满足适于作如谷物那样的干食物的包装材料时对水汽透过性（WVTR）的要求。还有，吹塑的高密度聚乙烯（HDPE）膜不表现出在食品包装，尤其是箱中袋型的包装时所希望的死折性。
本发明寻求提供有好的WVTR性，膜厚约为1密尔的HDPE膜，该膜也具有死折性而使之很适合于在立式装封（VFFS）机中进行的以箱中袋包装食物的操作。
因此，本发明提供一种至少含50%（重量）的密度为0.96或更高的高密度聚乙烯（HDPE），且在机器方向变形比为1.25∶1到2∶1而在横向为6∶1到12∶1的双轴取向高密度聚乙烯膜。最好横向变形比至少要比机器方向的变形比大4倍。
这里所用的“HDPE”表示密度为0.96或更高些的高密度聚乙烯。这种膜比吹塑的高密度聚乙烯膜有减小的WVTR，改善的死折性和其它明显较好的物理性质。当通过共挤塑或通过涂层提供一热封层时，该膜特别适用于包装，尤其是干食品的包装。
本发明的不等同双轴取向膜是用大份额的HDPE制备的。该膜可只含有单一的HDPE树脂，HDPE树脂的混合物或含有多到10%（重量）的小份额微晶蜡的HDPE。HDPE树脂的混合物有较好的加工性。无论用HDPE树脂的共混物或是用微晶蜡制成的膜都降低膜的劈裂性，而后者在立式装封（VFFS）机的操作中要导致膜的横向破裂。
HDPE聚合物的共混物可有利地含有ⅰ）大份额的熔体指数为0.5到2.0，最好为0.6到1.2的第一组分HDPE和ⅱ）熔体指数与第一组分HDPE不同的第二组分HDPE;最好是ⅱ）的熔体指数从0.1到0.5。
已发现三元共混物特别理想。合适的三元共混物通常含有50-98%（重量），最好是84-96%（重量）的熔体指数大于0.5到2.0的HDPE;1-25%（重量），最好是3-8%（重量）的熔体指数为0.1到0.5的HDPE;和1-25%（重量），最好是3-8%（重量），熔体指数大于2到大约8的HDPE。较好的是小份额的第2和第3组分HDPE聚合物以近似相等的量加入。
最好是本发明的不等同双轴取向HDPE膜至少在一面提供有可热封层。可热封层可用已知的方式加到HDPE上;例如在取向前用涂敷或共挤塑的方法或者在一个方向或两个方向的双轴取向操作后涂敷到HDPE上的方法。
可热封层可以是为此目的与聚烯烃膜尤其是聚乙烯膜结合在一起的任何一种惯用材料。例如可用乙烯-醋酸乙烯酯共聚物或乙烯-甲基丙烯酸盐离聚物（可从杜邦公司购到，牌号“Surlyn”）。已经发现可热封层是乙烯-甲基丙烯酸盐离聚物的膜特别适用于制备适于VFFS应用的膜。可热封层可含有这样的可热封树脂或可包含少量其它材料。例如，相对昂贵的Surlyn离聚物可与少量不太昂贵的材料如低密度聚乙烯相混。
本发明的HDPE膜除了热封层以外还可包括其它聚合物层或用它们来代替热封层;例如，包括对如氧气那样的气体有所希望的阻挡性质的聚合物。
本HDPE膜的取向度是本发明的一个重要方面，因为适当的取向度提供希望的物理性质、好的WVTR性和死折性。例如已测定本发明的厚度为1.0到1.2密尔的膜就有小于0.28的可接受的WVTR（克-密尔/100英寸2-24小时-1大气压），而对于吹塑HDPE膜则需要较大的厚度（厚度为1.5倍或更大）。减少了WVTR这种好处是由于双轴取向而得到的改进，也是由于在本发明中的铸塑挤出法比吹膜挤出能用更高密度的HDPE聚合物而得到的改进。在吹膜挤出中一般需要较低密度的HDPE聚合物，因为在实际工业方式中在吹膜法中较高密度树脂（密度大于约0.957）不能进行加工。虽然密度为0.957的高密度HDPE树脂或更高密度的树脂可用铸模挤出法直接制成薄膜，但卷边问题，均匀度，平展度和高WVTR仍然是有障碍的。因此大约0.8到1.5密尔厚的薄HDPE膜有最好的各种性能的平衡，尤其是对于VFFS应用，这是在本发明的不等同双轴取向膜中得到的，该膜是从铸塑厚度为12到20密尔的膜通过取向而减少到所希望的厚度而制备的。
该膜是以传统的方式制造和取向的。当HDPE膜囊幻嫔嫌锌扇确獠闶保ǔＳ糜腥龌蚋喙醯亩喙踝橄低惩瓿芍芗烦觥Ｔ贖DPE一边的辊有利地保持在大约65°而在热封面的温度大约为20℃。
膜以通常的方式加热到其取向温度且首先在两组压光辊之间受到机器方向（MD）取向，第二组辊以等于所希望的牵伸比的量、以大于第一组辊的速度转动。然后膜通过加热和在一个拉幅机架上受到横向牵伸而达到横向（TD）取向。典型的MD取向在60°到120℃进行而TD取向在110°到145℃下进行。
本发明也包括这里所述的膜在食品包装中的应用。
本发明的HDPE膜能在高到大约110英尺/分的铸塑速度下，即相当于在1.25倍MD取向下以140英尺/分的线速度进行高质量的生产。
本发明由下列实例说明，其中所有的份数除非另作规定均指重量。
实例1和2
通过共挤出占膜厚95%的基本HDPE层和占膜厚5%的Surlyn1652（从杜邦公司购的乙烯-甲基丙烯酸共聚物盐离聚物）层来制备终厚度为1密尔的两层双轴取向膜。用一个三辊组系统来制备这种膜，对着HDPE面的辊温为65℃而对着Surlyn面的辊温为20℃。然后将膜在约115℃下在MD方向作1.4倍取向，而在一个拉幅机架上在115-140℃下作横向的10倍取向。
实例1的HDPE是PE-5849（杜邦公司产，密度0.96，熔体指数1.0）。在实例2中90%（重量）的PE-5849与5%（重量）的PE-5925（杜邦公司产，密度0.96，熔体指数0.45）和5%（重量）的PE-7835（杜邦公司产，密度0.96，熔体指数3.0）共混。
实例2的膜表现出80-120℃的热粘期和卷封期，且在VFFS包装机上使用很好，而例1的膜则有过度的TD劈裂性不能使用。然而两种膜的物理性质却类似并总结在表1中。
表1
实例1    实例2
抗张强度    MD    6    6
（磅/英寸2×103） TD 16 20
模量    MD    365    380
（磅/英寸2×103） TD 490 570
刚度    MD    17    20
（克）    TD    21    24
撕裂强度    MD    89    63
（克/密尔）    TD    4    5
水汽透过率    0.23    0.24
（克-密尔/100英寸2/24小时，在1大气压下）
实例3-4
以和实例1相似的方式制备实例3的膜并与HDPE层含有4%（重量）微晶蜡的膜（实例4）作比较。实例3的膜具有105-120℃的热粘期和卷封期，但在VFFS机器上表现出很多TD劈裂使之不能用于此目的。实例4的膜具有90-120℃的热粘期和卷封期，不劈裂。
这些膜的物理性质总结在表2中：
表2
实例3    实例4
抗张强度    MD    5    5
（磅/英寸2×103） TD 37 35
模量    MD    330    340
（磅/英寸2） TD 740 730
刚度    MD    19    19
（克）    TD    32    31
撕裂强度    MD    50    44
（克/密尔）    TD    2    2
水汽透过率。    0.24    0.24
（克-密尔/100英寸2/24小时在1大气压下）

Claims (17)

1、一种双轴取向高密度聚乙烯膜，其中至少含有50%(重量)的密度为0.96或更高的高密度聚乙烯(HDPE)，膜在机器方向变形比从1.25∶1到2∶1而横向变形比从6∶1到12∶1。
2、按权利要求1的膜，其中在横向的变形比至少比在机器方向上的变形比大4倍。
3、按权利要求1或2的膜、其中包括ⅰ）大份额的熔体指数为0.5-2.0的第一组分HDPE和ⅱ）熔体指数不同于第一组分HDPE的第二组分HDPE。
4、按权利要求3的膜，其中ⅰ）熔体指数从0.6到1.2。
5、按权利要求3或4的膜，其中ⅱ）熔体指数从0.1到0.5。
6、按权利要求3到5中任一项的膜，它还包括ⅲ）熔体指数为2.0-8的第三组分HDPE。
7、按权利要求3到6中任一项的膜，其中ⅰ）包括50-98%（重量）的膜聚合物材料。
8、按权利要求3到7中任一项的膜，其中ⅱ）包括1-25%（重量）的膜聚合物材料。
9、按权利要求6到8中任一项的膜，其中ⅲ）包括1-25%（重量）的膜聚合物材料。
10、按权利要求6到9中任一项的膜，其中ⅰ）包括至少84%（重量），ⅱ）和ⅲ）每种包括3-8%（重量）的膜聚合物材料。
11、按权利要求1或2的膜，其中HDPE主要由单一树脂组成。
12、按权利要求1或2的膜，它包括高到10%（重量）的微晶蜡。
13、按前述任一权利要求的膜，其中至少在其一面有可热封层。
14、按权利要求13的膜;其中可热封层包括一种离聚物。
15、按权利要求13的膜，其中可热封层包括乙烯-醋酸乙烯酯共聚物。
16、按权利要求13到15中任一项的膜，其中可热封离聚物层被共挤出到所述HDPE膜的一个表面上。
17、按前述任一项权利要求的膜在食品包装中的应用。
CN88106971A 1987-09-28 1988-09-28 不等同双轴取向的高密度聚乙烯膜 Expired CN1014899B (zh)

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US101,894 1987-09-28
US07/101,894 US4870122A (en) 1987-09-28 1987-09-28 HdPE films with imbalanced biaxial orientation

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CN1014899B CN1014899B (zh) 1991-11-27

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JP (1) JP2573672B2 (zh)
KR (1) KR960015092B1 (zh)
CN (1) CN1014899B (zh)
AT (1) ATE77398T1 (zh)
AU (1) AU603702B2 (zh)
CA (1) CA1312435C (zh)
DE (1) DE3872140T2 (zh)
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AU603702B2 (en) 1990-11-22
DE3872140D1 (de) 1992-07-23
JPH01127316A (ja) 1989-05-19
US4870122A (en) 1989-09-26
ES2032564T3 (es) 1993-02-16
CA1312435C (en) 1993-01-12
JP2573672B2 (ja) 1997-01-22
PH25026A (en) 1991-01-28
AU2280388A (en) 1989-04-06
DE3872140T2 (de) 1992-12-03
CN1014899B (zh) 1991-11-27
EP0310290B1 (en) 1992-06-17
GR3004943T3 (zh) 1993-04-28
ATE77398T1 (de) 1992-07-15
EP0310290A1 (en) 1989-04-05
KR890005186A (ko) 1989-05-13
KR960015092B1 (ko) 1996-10-24

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