CN1442445A - 聚烯烃树脂组合物及使用该树脂组合物的收缩膜 - Google Patents

聚烯烃树脂组合物及使用该树脂组合物的收缩膜 Download PDF

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CN1442445A
CN1442445A CN03104526A CN03104526A CN1442445A CN 1442445 A CN1442445 A CN 1442445A CN 03104526 A CN03104526 A CN 03104526A CN 03104526 A CN03104526 A CN 03104526A CN 1442445 A CN1442445 A CN 1442445A
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高安裕
井上则英
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Abstract

本发明的聚烯烃树脂组合物的组成为：由丙烯和碳原子数为2～20的α－烯烃经无规共聚得到的聚合物、即由DSC测定的熔点范围为40～115℃、α－烯烃含量为5～70摩尔％的丙烯·α－烯烃无规共聚物(A)占10～100重量％，用DSC测定的熔点范围为120～150℃的无规聚丙烯树脂(B)占0～90重量％，以及相对于由上述(A)和(B)成分构成的组合物100重量份、在20～100℃的范围具有玻璃化转变点(Tg)、且数均分子量(Mn)为1000以下的脂环族饱和烃树脂(C)为5～100重量份。由本发明的聚烯烃树脂组合物得到的单层或多层膜，与现有产品相比，可在低温下拉伸，通过这样的低温拉伸得到的收缩膜不仅具有比高温拉伸得到的收缩膜更高的收缩率，且自然收缩率小。

Description

聚烯烃树脂组合物及使用该树脂组合物的收缩膜
技术领域
本发明主要涉及用于收缩标签的收缩膜用聚烯烃树脂组合物及其收缩膜。特别涉及低温下的收缩率、机械特性及光学特性优异的、且自然收缩性小的收缩膜。
背景技术
就广泛用于收缩膜的材质来说，人们非常熟悉的是聚氯乙烯系树脂、聚苯乙烯系树脂等。但是，由于担心这些树脂在废弃时的副产物对环境及人体造成不良影响，所以现在仍在进行开发使用聚烯烃的收缩膜。迄今为止，由聚烯烃系树脂制成的收缩膜与由聚氯乙烯系树脂制成的收缩膜相比，机械强度、低温下的热收缩率等很差。特别是将这种膜用作饮料用聚酯瓶的收缩标签使用时，该膜多是与聚酯瓶一起在使用蒸汽的收缩管道内进行收缩加工，因而需要可在更低温度下显示出高收缩率的收缩膜。而且，在再次回收聚酯瓶时，很多情况都是在聚酯树脂本身粉碎的同时，标签也被粉碎，利用它们相对于水的浮力差，采用液体比重分离法将聚酯树脂本体与标签树脂分开。例如，聚苯乙烯系树脂的比重大约为1.03～1.06，它会与比重为1.3～1.5的聚酯系树脂同时没入水中。因此，就这样使用上述方法将难以把使用比重为1以上的树脂的标签与聚酯系树脂分开。因此，人们希望得到一种比重小于1的、由聚烯烃制成的具有低温收缩性的收缩膜。
例如，特开2001-109429号公报中公开的“热收缩性聚丙烯系膜”中记载着共聚物单体含量为27％的聚丙烯系膜。但是，从低温下的热收缩性和透明性优异的膜方面以及从膜的刚性、耐热性等方面来看，都是不充分的。并且，如果要使由聚丙烯等聚烯烃制成的收缩膜达到高的热收缩率，自然收缩率(室温下经过一段时间后出现的收缩现象)也会增大。因此，人们希望得到一种热收缩率和自然收缩率能够取得很好的平衡的收缩膜。
发明内容
本发明的目的在于提供一种以刚性、透明性优异的聚丙烯系树脂为基材、在低温即80℃以下能拉伸的具有实用的外观的收缩标签用膜，这样得到的膜在80℃时的收缩率为30％以上，优选为35％以上，在90℃时的收缩率为40％以上，优选为超过45％。
为解决上述课题的收缩膜所用的树脂组合物是，由丙烯和碳原子数为2～20的α-烯烃经无规共聚得到的聚合物、即由示差扫描热量分析(DSC)测定的熔点范围为40～115℃、α-烯烃含量为5～70摩尔％的丙烯·α-烯烃无规共聚物(A)占10～100重量％，用DSC测定的熔点范围为120～150℃的无规聚丙烯树脂(B)占0～90重量％，而且相对于由上述(A)和(B)成分构成的组合物100重量份、在20～100℃的范围具有玻璃化转变点、且数均分子量为1000以下的脂环族饱和烃树脂(C)为5～100重量份。
本发明的收缩膜的特征在于：是由这些树脂组合物形成的单层构造的拉伸膜、或至少有一层是由这些树脂组合物形成的层的多层构造的拉伸膜。下面，详细说明本发明的收缩膜用聚烯烃树脂组合物的构成及其收缩膜。
收缩膜用树脂组合物是由丙烯·α-烯烃无规共聚物(A)、无规聚丙烯树脂(B)、和脂环族饱和烃树脂(C)构成的。
丙烯·α-烯烃无规共聚物(A)
作为本发明的收缩膜用聚烯烃树脂组合物的构成成分之一的丙烯·α-烯烃无规共聚物(A)，使用的是：用DSC测定的熔点范围为40～115℃、优选为65～110℃的、含有丙烯和5～70摩尔％、优选为20～50摩尔％的至少一种其它的α-烯烃的丙烯·α-烯烃无规共聚物。而且，共聚物(A)中的α-烯烃的含量是指由α-烯烃产生的结构单元的含量，该含量是由红外分光光度法求得的值。在制造这种丙烯·α-烯烃无规共聚物时所用的α-烯烃是指除丙烯以外的碳原子数从2到20的α-烯烃。作为这种α-烯烃，例如，可以举出乙烯以及1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯等，优选为乙烯及1-丁烯。
本发明所用的丙烯·α-烯烃无规共聚物(A)的密度(ASTM D 1505，23℃)通常为0.85～0.91g/cm3，优选为0.86～0.89g/cm3。并且，本发明所用的丙烯·α-烯烃无规共聚物(A)的熔融指数(MFR；ASTM D1238，230℃，2.16kg负荷)通常为0.1～20克/10分钟，优选为1～10克/10分钟。
在制造如上所述的丙烯·α-烯烃无规共聚物(A)时所用的聚合催化剂可以使用钛系或钒系的齐格勒·纳塔催化剂、或者钛系、锆系、铪系的茂金属催化剂、以及其它的用于烯烃聚合的公知的立构规正性催化剂。
由如上所述的丙烯·α-烯烃无规共聚物(A)的凝胶渗透色谱(GPC)求得的分子量分布(Mw/Mn)通常为5以下。并且，若对这种丙烯·α-烯烃无规共聚物，使用例如特开平7-138326号、WO 95/1417号等公报中所述的钛、锆、铪等过渡金属化合物的所谓茂金属系催化剂进行聚合，能够得到更低熔点且由凝胶渗透色谱(GPC)求得的分子量分布(Mw/Mn)为3以下的丙烯·α-烯烃无规共聚物，如果将它们用于本发明的收缩膜中，就可以得到低温下具有高收缩性能的收缩膜，而且可以看到透明性提高、表面的粘连性降低，因此可以优选利用。
无规聚丙烯树脂(B)
本发明所用的无规聚丙烯树脂(B)的用DSC测定的熔点范围为120～150℃，优选为130～140℃。本发明所用的无规聚丙烯树脂的熔融指数(MFR；ASTM D 1238、2.16kg负荷)通常为0.5～10克/10分钟，优选为2～8克/10分钟。如果熔点高于150℃，则延伸性降低，所以不宜选用，另外，如果熔点低于120℃，则会降低膜的机械性、耐热性等，所以也不宜选用。而且，这样的无规聚丙烯树脂(B)是通过丙烯和乙烯和/或丁烯等碳原子数为2～20的α-烯烃进行共聚而得到的。
脂环族饱和烃树脂(C)
本发明所用的脂环族饱和烃树脂，在20～100℃、优选为50～90℃的范围具有玻璃化转变点，数均分子量为1200以下，优选为600～1000。如果玻璃化转变点高于100℃，则会降低低温下的热收缩率，所以不宜选用，如果玻璃化转变点低于20℃，则膜的成型性恶化，且引起膜表面粘连，所以也不宜选用。
[聚烯烃树脂组合物]
本发明的聚烯烃树脂组合物是由丙烯·α-烯烃无规共聚物(A)和无规聚丙烯树脂(B)、以及脂环族饱和烃树脂(C)构成的。在聚烯烃树脂组合物中，丙烯·α-烯烃无规共聚物(A)所占比例通常为10～100重量％，优选为20～70重量％，无规聚丙烯树脂(B)所占比例通常为0～90重量％，优选为30～80重量％。并且，在聚烯烃树脂组合物中，脂环族饱和烃树脂(C)所占比例是，相对于以由上述(A)和(B)成分构成的组合物100重量份，通常为5～100重量份，优选为25～75重量份。在不损害本发明的目的的范围内，还可以在其中添加耐热稳定剂、防氧化剂、紫外线吸收剂、抗粘连剂、滑爽剂、防静电剂、耐气候稳定剂、防雾剂、结晶成核剂、碱吸收剂、润滑剂、阻燃剂等。
[单层或多层膜]
单层或多层膜
本发明的单层或多层膜是由聚烯烃树脂组合物形成的单层或多层结构的膜。这种膜可以使用吹塑成型法、T-模压成型法等众所周知的成型方法制成，厚度通常为50～500μm。
层压膜
本发明的层压膜是在聚烯烃树脂组合物的单面或两面上层压其它的膜而形成的膜。对于层压形成的膜没有特别的限定，以特开2000-246797中提出的环状聚烯烃系树脂为代表，可以举出聚乙烯、聚丙烯、乙烯·乙酸乙烯共聚物、乙烯·丙烯酸共聚物、乙烯·甲基丙烯酸甲酯共聚物等聚烯烃膜、苯乙烯系树脂膜、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等聚酯系膜、尼龙6、尼龙66这样的聚酰胺膜、以及乙烯·乙烯醇共聚物膜等。
就层压这样的膜的方法来说，可以举出挤出层压法、使用中介涂层剂的干式层压法。
层压膜的厚度通常为50～500μm.。
[收缩膜]
本发明的收缩膜可以将由聚烯烃树脂组合物形成的上述膜在60℃～100℃、优选为60℃～80℃范围内沿某一辊或双辊拉伸而得。拉伸方法可以使用现在常用的聚烯烃树脂膜的拉伸方法，例如对通过加热辊进行单辊拉伸、双辊拉伸方法来说，可以用通过管式(tubular)法的同时双辊拉伸法或加热辊/拉幅机的顺次双辊拉伸法进行成型。拉伸倍数没有特别的限定，通常为3～10倍，优选为4～8倍。拉伸膜的厚度通常为10～200μm.。
这样的拉伸膜可以适合用作本发明的收缩膜，经80℃的收缩试验测定的热收缩率为30％以上，优选为35％以上，且经90℃的收缩试验测定的热收缩率为40％以上，优选为45％以上，在40℃时测定的自然收缩试验中，自然收缩率(室温下经过一段时间后出现的收缩现象)为6％以下，优选为4％以下。
具体实施方式
【实施例】
实施例和比较例中所用的膜原料成分如下所示。
丙烯·α-烯烃无规共聚物(A)
○三井化学(株)制丙烯·1-丁烯无规共聚物(商品名“XR110T”)(A1)
·丁烯含量＝26摩尔％
·MFR(ASTM D 1238，230℃，2.16kg)＝6.0克/10分钟
·熔点＝110℃
·Mw/Mn＝4.50
○根据特开平7-13826号中所述的茂金属系催化剂及聚合方法制造的丙烯·1-丁烯无规共聚物(A2)
·丁烯含量＝30摩尔％
·MFR(ASTM D 1238，230℃，2.16kg)＝4.9克/10分钟
·熔点＝85℃
·Mw/Mn＝1.97
○根据特开平7-13826号中所述的茂金属系催化剂及聚合方法制造的丙烯·1-丁烯无规共聚物(A3)
·丁烯含量＝43.3摩尔％
·MFR(ASTM D 1238，230℃，2.16kg)＝6.7克/10分钟
·熔点＝72℃
·Mw/Mn＝1.85
无规聚丙烯树脂(B)
○无规聚丙烯(B1)
·乙烯含量＝4.2摩尔％
·MFR(ASTM D 1238，230℃，2.16kg)＝2.7克/10分钟
·熔点＝135℃
脂环族饱和烃树脂(C)
○荒川化学社制的石油树脂(商品名“P125”)(C1)
·Mn＝820
·Tg(玻璃化转变温度)＝80℃
○荒川化学社制的石油树脂(商品名“P140”)(C2)
·Mn＝970
·Tg(玻璃化转变温度)＝90℃
实施例和比较例得到的拉伸膜的收缩率试验按照下述方法进行。
将由拉伸膜裁成15mm×150mm(拉伸方向)得到的试验样品浸入80℃和90℃的温水中10秒钟，根据该热处理前后的膜尺寸差值，由式(1)求得热收缩率。另一方面，自然收缩率是，将与热收缩率试验同样大小的试验样品，在常压条件下、使用40℃的烘箱进行5天的老化试验，根据老化试验前后的膜的尺寸差值，由式(1)求得自然收缩率。
【式1】
Figure A0310452600081
(实施例1)
将由上述丙烯·1-丁烯无规共聚物(A1)25重量％和无规聚丙烯(B1)75重量％构成的树脂组合物、和相对于100重量份上述组合物为30重量份的石油树脂(C1)，用造粒机混合进行造粒。然后，一边将得到的颗粒用铸膜成型机在200℃温度下挤出，一边制成250μm厚的单层膜。从这层膜上切下9cm见方的片，用台式双轴拉伸试验机沿某一轴向拉伸。在规定温度下预热两分钟后，以1米/分钟的速度拉伸到原长的5倍。对这样得到的拉伸薄膜使用上述实验法进行收缩率测定。结果表示在表1中。
(实施例2)
将由上述丙烯·1-丁烯无规共聚物(A2)50重量％和无规聚丙烯(B1)50重量％构成的组合物、和相对于100重量份上述组合物为15重量份的石油树脂(C2)，用与实施例1相同的方法制膜、拉伸，制得单轴拉伸样品。对这样得到的拉伸薄膜使用与实施例1同样的实验法进行收缩率测定。结果表示在表1中。
(实施例3)
将由上述丙烯·1-丁烯无规共聚物(A3)25重量％和无规聚丙烯(B1)75重量％构成的组合物、和相对于100重量份上述组合物为20重量份的石油树脂(C2)，用与实施例1相同的方法制膜、拉伸，制得单轴拉伸样品。对这样得到的拉伸薄膜使用与实施例1同样的实验法进行收缩率测定。结果表示在表1中。
(实施例4)
将由上述丙烯·1-丁烯无规共聚物(A3)50重量％和无规聚丙烯(B1)50重量％构成的组合物、和相对于100重量份上述组合物为15重量份的石油树脂(C2)，用与实施例1相同的方法制膜、拉伸，制得单轴拉伸样品。对这样得到的拉伸薄膜使用与实施例1同样的实验法进行收缩率测定。结果表示在表1中。
(比较例1)
将100重量份无规聚丙烯(B1)和25重量份的石油树脂(C2)，用与实施例1相同的方法制膜、拉伸，制得单轴拉伸样品。对这样得到的拉伸薄膜使用与实施例1同样的实验法进行收缩率测定。结果表示在表1中。
【表1】
树脂组成      热收缩率(％)   自然收缩(％)
     拉伸温度70℃
   (A1)    (A2)    (A3)    (B1)    (C1)*    (C2)*     80℃     90℃    40℃×5天
实施例1     25     0     0     75     30     0     31.3     43.3    4
实施例2     0     50     0     50     0     15     31.3     45.3    1.3
实施例3     0     0     25     75     0     20     30     42    3.3
实施例4     0     0     50     50     0     15     40     49.3    1.3
比较例1     0     0     0     100     0     25     21.3     32.7    3.3
*表示相对于(A)和(B)的合计100重量份的重量份。
通过在实施例1中添加约30重量份的玻璃化转变温度低(80℃)的石油树脂(アルコン)(C1)，在80℃时的收缩率达到31.3％，在90℃时的收缩率达到43.3％。在实施例2中，由于无规聚丙烯(B1)的量和丙烯·1-丁烯无规共聚物(A2)的量相等，所以在80℃时的收缩率达到31.3％，在90℃时的收缩率达到45.3％。在实施例3中，由于丙烯·1-丁烯无规共聚物(A3)的熔点低于实施例2中所用的丙烯·1-丁烯无规共聚物(A2)的熔点，所以即使减少它们相对于无规聚丙烯(B1)的量，在80℃时的收缩率也可达到30.0％，在90℃时的收缩率达到42.0％。并且如实施例4所示，与实施例3相比，通过增加丙烯·1-丁烯无规共聚物(A3)，还能提高收缩率。另一方面，如比较例1所示，当未使用丙烯·1-丁烯无规共聚物时，不能达到80℃时收缩率为30％以上、90℃时收缩率为40％以上这样的目标值。对于自然收缩率来说，实施例2、4，即丙烯·1-丁烯共聚物(A2)、(A3)的混合量越多，自然收缩率越小。
按照本发明，由于使用丙烯·1-丁烯无规共聚物、优选为经茂金属催化而聚合的低熔点的且组成狭、分子量分布窄的丙烯·1-丁烯无规共聚物，在可进行低温拉伸的同时，实现了低温下的收缩特性优异的收缩标签用膜。

Claims (4)

1.一种聚烯烃树脂组合物，其特征在于：由丙烯和碳原子数为2～20的α-烯烃经无规共聚得到的聚合物、即由示差扫描热量分析(DSC)测定的熔点范围为40～115℃、α-烯烃含量为5～70摩尔％的丙烯·α-烯烃无规共聚物(A)占10～100重量％，用DSC测定的熔点范围为120～150℃的无规聚丙烯树脂(B)占0～90重量％，以及相对于由上述(A)和(B)成分构成的组合物100重量份、在20～100℃的范围具有玻璃化转变点、且数均分子量为1000以下的脂环族饱和烃树脂(C)为5～100重量份。
2.一种至少有一层是由权利要求1所述的树脂组合物形成的膜、厚度为50～500μm的单层或多层膜。
3.一种厚度为50～500μm的层压膜，其特征在于：将选自聚烯烃膜、聚苯乙烯膜、聚酯膜、聚酰胺膜、由粘合性聚烯烃和阻透性树脂形成的层压体中的至少一种，层压在由权利要求1所述的树脂组合物形成的膜的单面或两面上。
4.一种将权利要求2或3所述的单层或多层膜、或层压膜至少朝某一轴向乃至双轴向拉伸至3倍以上得到的收缩膜。
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US8137773B2 (en) 2005-11-30 2012-03-20 Mitsubishi Plastics, Inc. Polyolefin series heat-shrinkable film, molded product and heat-shrinkable laminated label employing the film, and container
CN101316708B (zh) * 2005-11-30 2012-08-22 三菱树脂株式会社 聚烯烃类热收缩性薄膜、使用该薄膜的成型品、热收缩性标签和容器
US7884159B2 (en) 2006-02-01 2011-02-08 Mitsui Chemicals, Inc. Propylene polymer composition, film, stretched film, shrink film and a method for producing shrink package
CN101379128B (zh) * 2006-02-01 2011-11-16 三井化学株式会社 丙烯聚合物组合物、膜、拉伸膜、收缩膜、收缩包装体的制造方法
CN102036817A (zh) * 2008-05-22 2011-04-27 埃克森美孚石油公司 基于聚丙烯的收缩薄膜
US10005262B2 (en) 2011-12-30 2018-06-26 Guangdong Decro Film New Materials Co., Ltd. Heat shrinkable polyolefin film and a preparation method thereof

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JP4068978B2 (ja) 2008-03-26
AU2003200487C1 (en) 2003-08-28
AU2003200487A1 (en) 2003-08-28
DE60323172D1 (de) 2008-10-09
KR20030068469A (ko) 2003-08-21
EP1336641A1 (en) 2003-08-20
EP1336641B1 (en) 2008-08-27
CN1284821C (zh) 2006-11-15
AU2003200487B2 (en) 2006-10-12
KR100491456B1 (ko) 2005-05-25
JP2003306587A (ja) 2003-10-31
US6855406B2 (en) 2005-02-15

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