CN1123224A - 丙烯聚合物流延薄膜 - Google Patents

丙烯聚合物流延薄膜 Download PDF

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CN1123224A
CN1123224A CN94109549A CN94109549A CN1123224A CN 1123224 A CN1123224 A CN 1123224A CN 94109549 A CN94109549 A CN 94109549A CN 94109549 A CN94109549 A CN 94109549A CN 1123224 A CN1123224 A CN 1123224A
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propylene
copolymer
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olefin
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CN1053615C (zh
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P·库斯曼斯
G·列斯卡
D·罗曼尼尼
R·坦甘奈利
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Himont Inc
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32—LAYERED PRODUCTS
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    • B32—LAYERED PRODUCTS
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract

一种多层流延薄膜，它包括：A)至少一层基本上由下述物质组成：C3-C6α-烯烃的结晶均聚物，或丙烯与乙烯和/或C4-C10α-烯烃的无规共聚物，或丙烯与乙烯和/或C4-C8α-烯烃的晶状无规共聚物的组合物(组分A)；和B)至少一层基本上由下述物质组成：丙烯均聚物，或丙烯与乙烯或C4-C10α-烯烃的共聚物，或丙烯与乙烯和C4-C10α-烯烃的共聚物(B组分)，所述均聚物和共聚物断裂伸长率低于30％；所述薄膜的断裂伸长率大于100％。

Description

丙烯聚合物流延薄膜
本发明涉及多层聚丙烯流延薄膜，它具有改进的可折性特征，本发明尤其涉及多层聚丙烯流延薄膜，其中至少一层比起其它层来有较高的刚性和/或较低的断裂伸长率。
由于它们的机械和物理性能，本发明的多层薄膜特别适合用于包装领域，尤其在糖果包装方面。
本领域技术人员公知多层薄膜可用于各个领域，尤其在食品包装方面。仅仅使用丙聚均聚物生产出来的薄膜存在一些缺陷如脆性，无法保持折皱性以及较差的耐冲击性。
为了克服聚丙烯薄膜的上述缺点，所用聚丙烯必须有一些特别的性能(如见公开的欧洲专利申请EP-A-432452)，或者将它与氢化树脂共挤压(如见公开的欧洲专利EP-A544632)。
欧洲专利申请EP-A432452描述了单层和多层聚丙烯和丙烯共聚物的单取向薄膜，它既有透光度又有保持折皱的能力。所述专利申请告诉我们通过使用具有狭窄分子量分布的丙烯均聚物或共聚物可以获得后一特性。
如今已发现具有很好折皱性能的、因而可很好保持折皱的新薄膜。所述性能使本发明的薄膜特别适用于包装领域，特别是上述的用途。
与上述EP-A-432452专利申请提到的丙烯均聚物和共聚物不同，现已发现也是构成本发明薄膜中一层的均聚物和共聚物，事实上它们有很宽的分子量分布，而且有着使它们可保持折皱性的物理-机械特性。
本发明的薄膜的附加优点是它们有良的透光度。本发明薄膜的又一优点是当所述薄膜含有一些下面将详述的聚合物时，它们也显示出良好的热合性能。这后一优点使得必要时人们可获得包装物品的气密封，这对一些用途将是有价值的。
本发明薄膜还有另一个优点即气密性，因而保证了被裹在里面的产品有较长的保存期。
因此，本发明提供一种多层流延薄膜，它包括：
A)至少一层基本上由下述物质组成：C3-C6α-烯烃的结晶均聚物，或丙烯与乙烯和/或C4-C10α-烯烃的无规共聚物，或丙烯与乙烯和/或C4-C8α-烯烃的结晶无规共聚物的组合物(组分A)；以及
B)至少一层基本上由下述物质组成：丙烯均聚物，或丙烯与乙烯或C4-C10α-烯烃的共聚物，或丙烯与乙烯和C4-C10α-烯烃的共聚物，所述均聚物和共聚物断裂伸长率低于30％(组分B)；所述薄膜断裂伸长率大于100％，优选大于200％，更优选大于500％。
优选地，组分A的断裂伸长率大于350％，更优选大于500％；另一方面，对于组分B，最好其断裂伸长率低于25％。还有，组分B的挠曲模量(FM)优选大于1600MPa，更优选大于2000MPa。
在本发明的一个实施例中，所述薄膜仅包含两层，确切地说即一层组分B与一层组分A结合。
优选的薄膜由三导组成，在这种情况下组分B置于两层组分A中间，或者组分A置于两层组分B中间。优选的组合体是当组分B量于中间时组分A构成两个外层。
组分A优选为丙烯结晶无规共聚物的组合物，其中共聚单体为乙烯和/或C4-C8α-烯烃。所述组合物优选地包含以下物质(重量百分比)：
1)30-65％，优选35-65％，更优选45-65％的丙烯与C4-C8α烯烃的共聚物，含有80-98％，优选85-95％的丙烯；和
2)35-70％，优选35-65％，更优选35-55％的丙烯共聚物与2-10％，优选7-9％的乙烯；或者丙烯与0.5-5％，优选1-3％的乙烯和2-10％，优选3-6％的C4-C8α-烯烃的共聚物。
如先前所述，组分A也可以是均聚物，如丙烯、1-丁烯或4-甲基-1-戊烯的均聚物，或丙烯的共聚物。特别适合于组分A的丙烯共聚物的具体例子有：
1)丙烯的结晶无规共聚物，含有1.5-20(重量)的乙烯或C4-C8α-烯烃；和
2)丙烯的结晶无规共聚物，含有85-96％(重量)丙烯，1.5-5％(重量)乙烯和2.5-10％(重量)的C4-C8α-烯烃。
构成组分A的均聚物和共聚物经单级聚合或多级连续聚合，使用Ziegler-Natta催化剂来制得。
组分A共聚物的实例见述于本申请人的公开的欧洲专利申请EP-A0483523，EP-A0560326。
组分B可以是另一种丙烯均聚物，或是丙烯与乙烯和/或一种或多种α-烯烃、优选C4-C8烯烃的无规共聚物或是多相共聚物。
一般而言，包含带有低断裂伸度率特征并常常是较高挠曲模量值的组分B的聚合物和共聚物，是在单级或多级聚合作用中，使用高立构定向度的Ziegler-Natta催化剂来制得的。因此，该聚合产物的全同立构指数相对较高，一般大于或等于94％，优选大于或等或96％(在二甲苯溶液中，25℃时测量)。还有，分子量分布一般较宽，Mw/Mn值优选为8-30(Mw和Mn分别指重均分子量和散均分子量)。上述聚合物的实施例见述于于本申请人的欧洲专利申请EP-A-0573862，欧洲专利申请EP-A0098077以及日本公开专利申请59-172507。
用于本发明的适用于与丙烯共聚合以获得组分A和B共聚物的C4-C8α-烯烃包括线形或支化α-烯烃，如1-丁烯，1-戊烯，1-己烯，1-辛烯，3-甲基-1-戊烯，4-甲基-1-戊烯，和3-甲基-1-己烯。优选的α-烯烃为1-丁烯。
如果共聚单体为乙烯，则共聚物B中的共聚单体的数量优选地为总聚合物的0.5-2％(重量)；如果共聚物单体为C4-C8α-烯烃，所述数量优选为0.5-5％。
为了获得有良好热合性能的流延薄膜，从丙烯共聚物中优选A，其中所含共聚单体乙烯为1-3％和丁烯5-10％。
可以加入不同的添加剂如稳定剂、颜料到用于制造本发明薄膜的聚合物中。
本发明薄膜的厚度优选为10-100μm，更优选20-50μm。
在本发明的三层薄膜中，中间一层的厚度优选为总厚度的一半，而每个外层的厚度为剩余厚度的一半。
本发明的多层流延薄膜用常规制造条件经薄膜共挤压而结合来制得。
下面是实施例中分析所采用的分析方法：
-M·I：根据ASTM D 1238，条件L测定；
-23℃的FM：根据ASTMD 790测定；
-屈服和断裂的抗张强度：根据ASTM D-882测定，试验速率为50mm/min；
-屈服和断裂的伸长率：根据ASTM D-882测定，试验速率为50mm/min。
还有，实施例中的薄膜都经受以下试验：
-扭曲滞留量试验：该试验是将一个直经为15mm的钢球象包糖果一样用手包在一片150×60mm本发明的薄膜中。薄膜的两端朝相反方向扭曲。一端扭540°(1转)，另一端扭1080°(3转)。30秒钟后测定扭曲角以决定滞留程度。
下述实施仅用于说明而本发明不限于此：
实施例中所用聚合物组分：
1)全同立构指数为98.5的丙烯均聚物；
2)全同立构指数为96.5的丙烯均聚物；
3)组成如下的无规共聚物组合物：50％含有4％乙烯的丙烯/乙烯无规共聚物，50％含有16％1-丁烯的丙烯/1-丁烯无规共聚物。在载于活性氯化镁，具有高立构定向度的Ziegler Natta催化剂的存在下经连续聚合作用获得所述组合物。
所述聚合物的物理性能列于表1
实施例1：
通过共挤压(用三台DOLCI挤出机，在240-255℃的不同温度下操作与一平板挤出口模相连)做成40μm厚的三层流延薄膜，其中间层是均聚物薄膜(1)，而两外层为丙烯均聚物构成的薄膜(2)。中间层的厚度为外层厚度的两倍。
实施例2：
如实施例1的方法制得一薄膜，唯一不同即该实施例中的薄膜厚度为25μm。
实施例3：
用DOLCI挤出机制得40μm三层流延薄膜，其中间层为均聚物薄膜(1)，而外两层由丙烯无规共聚物(3)构成。中间层的厚度为外层厚度的两倍。
实施例4：
如实施例3的方法制得一薄膜，唯一不同即该实施例中的薄膜厚度为25μm。
比较例1(1C)：
使用25μm厚的薄膜，所述薄膜由用无定形、低分子量、玻璃状烃类树脂改性的双取向全同聚丙烯组成。
实施例和比较例中的薄膜特征示于表2，其中MD和CD分别指纵向和横向。
表3显示了薄膜在扭曲刚结束和30秒后的扭曲滞留程度。
                              表1
    聚合物性能    均聚物    (1)     均聚物    (2)     均聚物    (3)
 M.I.(g/10min)     3.7     11     6
 F.M.(MPa)     2300     1600     780
 屈服应力(MPa)     40     35     23
 屈服伸长率(％)     5     11     15
 断裂伸长率(％)     20     370     ＞500
                               表2
实施例和比较例 FM(MPa) 屈服 断裂：
应力(MPa) 伸长率.(％) 应力(MPa) 伸长率.(％)
    1     796MD     24.1MD     10.3MD     54.6MD     579MD
    717CD     21.8CD      8.9CD     30.8CD     757CD
    2     788MD     25.0MD     11.0MD     58.2MD     610MD
    710CD     21.0CD      8.0CD     32.1CD     760CD
    3     788CD     25.0MD     11.1MD     57.6MD     481MD
    770CD     23.3CD      8.6CD     30.5CD     757CD
    4     760MD     23.1MD      9.1MD     53.0MD     620MD
    705CD     22.0CD      8.6CD     31.0CD     720CD
    1c    3500MD     --       --    199.0MD      18MD
   1770CD     --       --     81.2CD      76CD
                           表3
实施例和比较例     扭曲滞留量
     刚结束(540°扭曲)    30秒后(1080°扭曲)
    1     360     900
    2     360     720
    3     360     540
    4     360     720
    1c     180     360

Claims (10)

1.一种多层流延薄膜，它包括：
A)至少一层基本上由下述物质组成：C3-C6α-烯烃的结晶均聚物，或丙烯与乙烯和/或C4-C10α-烯烃的无规共聚物，或丙烯与乙烯和/或C4-C8α-烯烃的晶状无规共聚物的组合物(组分A)；和
B)至少一层基本上由下述物质组成：丙烯均聚物，或丙烯与乙烯或C4-C10α-烯烃的共聚物，或丙烯与乙烯和C4-C10α-烯烃的共聚物；所述均聚物和共聚物断裂伸长率低于30％(组分B)；
所述薄膜的断裂伸长率大于100％。
2.权利要求1的薄膜，其中组分B的断裂伸长率低于25％。
3.权利要求1的薄膜，其断裂伸长率大于200％。
4.权利要求1的薄膜，其中组分A是丙烯与乙烯的共聚物。
5.权利要求1的薄膜，其中组分A是丙烯与乙烯和1-丁烯的共聚物。
6.权利要求5的薄膜，其中1-丁烯含量为2-10％(重量)，乙烯含量为0.5-5％(重量)。
7.权利要求1的薄膜，其中组分B是丙烯均聚物。
8.权利要求1的薄膜，其中组分B是共聚物，它含有0.5-2％(重量)的乙烯。
9.权利要求1的薄膜，其中组分B是共聚物，它含有0.5-5％(重量)的C4-C8α-烯烃。
10.权利要求1的薄膜用于包装。
CN94109549A 1993-08-11 1994-08-11 丙烯聚合物流延薄膜 Expired - Fee Related CN1053615C (zh)

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ITMI931815A IT1271418B (it) 1993-08-11 1993-08-11 Manufatti in film cast costituiti da polimeri propilenici
ITMI93A001815 1993-08-11

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CN1123224A true CN1123224A (zh) 1996-05-29
CN1053615C CN1053615C (zh) 2000-06-21

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US6440533B1 (en) 2000-09-22 2002-08-27 Tredegar Film Products Corporation PVC replacement film
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EP0638415B1 (en) 2000-03-29
ATE191178T1 (de) 2000-04-15
JPH07164606A (ja) 1995-06-27
IT1271418B (it) 1997-05-28
ITMI931815A0 (it) 1993-08-11
EP0638415A1 (en) 1995-02-15
DE69423680T2 (de) 2000-08-17
US5741565A (en) 1998-04-21
KR950005542A (ko) 1995-03-20
CN1053615C (zh) 2000-06-21
JP4297517B2 (ja) 2009-07-15
ITMI931815A1 (it) 1995-02-11
DE69423680D1 (de) 2000-05-04

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