CN1073131C - 粘性聚丙烯树脂组合物及使用该树脂组合物的多层层合体 - Google Patents

粘性聚丙烯树脂组合物及使用该树脂组合物的多层层合体 Download PDF

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CN1073131C
CN1073131C CN96109985A CN96109985A CN1073131C CN 1073131 C CN1073131 C CN 1073131C CN 96109985 A CN96109985 A CN 96109985A CN 96109985 A CN96109985 A CN 96109985A CN 1073131 C CN1073131 C CN 1073131C
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田中晴彦
河内秀史
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Mitsui Petrochemical Industries Ltd
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Abstract

本发明揭示(1)一种含如下组分的粘性聚丙烯树脂组合物：(a)50-90重量份改性聚丙烯或合上述改性聚丙烯的组合物，上述改性聚丙烯用至少一种选自不饱和羧酸及其衍生物的单体接技改性；和(b)10-50重量份不同于改性聚丙烯或组合物(a)的改性聚烯烃，上述改性聚烯烃用至少一种选自不饱和羧酸及其衍生物的单体接枝改性；(2)含这种组合物的多层层合体。组合物(1)对聚烯烃树脂层和聚酰胺树脂和/或乙烯/乙烯醇共聚物树脂层具有极好的粘合力。

Description

粘性聚丙烯树脂组合物及使用该树脂组合物的多层层合体
发明的背景
发明领域
本发明涉及一种粘性的聚丙烯树脂组合物和使用该树脂组合物的多层层合体。
更具体地说，本发明涉及适于将聚烯烃层如聚丙烯层与聚酰胺树脂和/或乙烯/乙烯醇共聚物层粘合在一起的粘性聚丙烯树脂组合物，还涉及将上述组合物用作粘合层的多层层合体。
现有技术的描述
迄今已知聚烯烃如聚丙烯和聚酰胺树脂的层压薄膜、聚烯烃如聚丙烯与乙烯/乙烯醇共聚物的层压薄膜，以及各种用作粘合层的材料。
然而，这些材料在制备收缩薄膜的拉伸步骤中很大程度上失去粘合力，因此不能按需提供令人满意的粘合力。
发明的概述
本发明的目的是提供对聚烯烃如聚丙烯和聚酰胺树脂和/或乙烯/乙烯醇共聚物具有极好粘合力的粘性聚丙烯树脂组合物。
本发明的另一个目的是提供在聚烯烃层与聚酰胺和/或乙烯/乙烯醇共聚物层之间具有由上述本发明粘性聚丙烯树脂组合物制成的粘合层的多层层合体。
本发明的再一个目的是提供含有在未拉伸状态和拉伸状态具有极好粘合力的粘合层的多层层合体。该粘合层由上述的本发明粘性聚丙烯树脂组合物制成。
根据本发明，提供一种含如下组分的粘性聚丙烯树脂组合物：
(a)50-90重量份改性聚丙烯或含上述改性聚丙烯的组合物，上述改性聚丙烯用至少一种选自不饱和羧酸及其衍生物的单体接枝改性；和
(b)10-50重量份不同于改性聚丙烯(a)的改性聚烯烃，上述改性聚烯烃用至少一种选自不饱和羧酸及其衍生物的单体接枝改性。
另外，根据本发明提供一种不少于3层的多层层合体，在上述层合体中依次层压聚烯烃层、含上述粘性聚丙烯树脂组合物的粘合层以及聚酰胺和/或乙烯/乙烯醇共聚物层。本发明的优选实施方案
在本发明粘性聚丙烯树脂组合物中，作为改性聚丙烯树脂(a)的基础聚合物的聚丙烯是熔点高于130℃，但低于170℃的丙烯均聚物、或含不少于93摩尔％丙烯和另一种a-烯烃的丙烯共聚物。
当使用共聚物时，用作另一种a-烯烃共单体的为：乙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯或1-癸烯。
聚丙烯或共聚物的熔体流动速率(在230℃按ASTM D1238测量)较好为0.1-100克/10分钟，更好为0.5-50克/10分钟。
不饱和羧酸或其衍生物可用作接枝单体。用作不饱和羧酸的具体例子为：丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸。用作不饱和羧酸衍生物的可以列举酸酐、酯、酰胺、酰亚胺和金属盐。具体的例子包括马来酸酐、5-降冰片烷-2,3-二羧酸酐、衣康酸酐、柠檬酸酐、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸缩水甘油酯、马来酸一乙酯、马来酸二乙酯、富马酸一甲酯、富马酸二甲酯、衣康酸一甲酯、衣康酸二乙酯、丙烯酰胺、甲基丙烯酰胺、马来酸一酰胺、马来酸二酰胺、N-一乙基马来酰胺、N,N-二乙基马来酰胺、N-一丁基马来酰胺、N,N-二丁基马来酰胺、富马酸一酰胺、富马酸二酰胺、N-一丁基富马酰胺、N,N-二丁基富马酰胺、马来酰亚胺、N-丁基马来酰亚胺、N苯基富马酰亚胺、丙烯酸钠、甲基丙烯酸钠、丙烯酸钾和甲基丙烯酸钾。在这些接枝单体中，最好使用马来酸酐或5-降冰片烷-2,3-二羧酸酐。
用不饱和羧酸或其衍生物改性的优选改性聚丙烯是用0.05-15重量％，最好用0.1-10重量％的不饱和羧酸或其衍生物接枝改性的聚丙烯、以改性前聚丙烯为基准。本发明的组分可以仅由接枝改性聚丙烯构成，或是未改性聚丙烯和接枝改性聚丙烯的组合物。
改性聚烯烃(b)是将聚乙烯、聚丁烯、乙烯/a-烯烃共聚物(乙烯含量不大于7摩尔％的乙烯-丙烯共聚物除外)等用作基础树脂并用不饱和羧酸或其衍生物接枝改性的接枝改性聚烯烃，以及优选地，(ⅰ)改性聚烯烃(b)的密度为0.860-0.930克/厘米3，最好为0.860-0.905克/厘米3，(ⅱ)它在190℃和2.16公斤负载下的熔体流动速率(MFR)为0.1-50克/10分钟，最好为0.1-10克/10分钟，(ⅲ)它的接枝率为0.01-5重量％，最好为0.3-3重量％。
改性聚烯烃更好是将基本上为无定形或结晶度低的乙烯/a-烯烃共聚物用作基础树脂。改性乙烯/a-烯烃共聚物(b)的基础聚合物优选为乙烯和含3-20个碳原子的a-烯烃的无规共聚物。优选的a-烯烃含有3-10个碳原子。a-烯烃的优选实例包括丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯、1-癸烯等。
乙烯/a-烯烃共聚物(b)可用已知的使用钛(Ti)、钒(V)或锆(Zr)型催化剂的方法制备。
乙烯/a-烯烃共聚物(b)最好含有95-70摩尔％，更好为90-75摩尔％的乙烯所固有的聚合物单元。
乙烯/a-烯烃共聚物(b)基本上是无定形的或结晶度低的，它的结晶度(用X射线衍射法测量)最好不超过40％。
许多已知的方法可用于制备由聚烯烃与接枝单体接枝共聚而得的改性产物。例如，可以提到熔体改性方法和溶液改性方法。在熔体改性方法中将聚烯烃用挤塑机熔化，并与接枝单体接枝共聚；在溶液改性方法中加入溶于溶剂的接枝单体，使聚烯烃接枝共聚。在两种方法中，为了使接枝单体有效地接枝共聚，需要在自由基引发剂的存在下引发反应。接枝反应一般在60-350℃的温度下进行。自由基引发剂的用量一般为0.001-1重量份/100重量份聚烯烃。用作自由基引发剂可以有：有机过氧化物、有机过酸酯，如过氧化苯甲酰、过氧化二氯苯甲酰、过氧化二异丙苯基、过氧化二叔丁基、2,5-二甲基-2,5-二(过氧苯甲酰氧基)己炔-3[2.5-dimethyl-2,5-di(peroxide benzoate)hexyne-3)、1,4-二(叔丁基过氧化异丙基)苯[1,4-bis(tert-butylperoxyisopropyl)benzene］、过氧化月桂酰、过乙酸叔丁酯、2,5-二甲基-2,5-双过氧化叔丁基己炔-3、2,5-二甲基-2,5-双过氧化叔丁基己烷、过苯甲酸叔丁酯、乙酸叔丁基过苯酯(terr-butyl perphenyl acetate)、过异丁酸叔丁酯、过仲辛酸叔丁酯、过新戊酸叔丁酯、过新戊酸异丙苯酯、乙酸叔丁基过二乙酯(tert-butyl perdiethyl acetate)、或其它偶氮化合物如偶氮异丁腈或偶氮异丁酸二甲酯(dimethylazoisobutylate)等。在这些引发剂中优选使用过氧化二烷基、如过氧化二异丙苯基、过氧化二叔丁基、2,5-二甲基-2,5-二(过氧苯甲酰氧基)己炔-3、2,5-二甲基-2,5双过氧化叔丁基己烷或1,4-二(叔丁基过氧化异丙基)苯。在反应过程中，可以存在其它单体如苯乙烯。
需调节接枝到聚烯烃上的接枝单体的量(下文称为接枝率)，使组合物的总接枝率为10-4-5重量％。从工业的观点来看，需要先制备接枝率为10-2-6重量％的改性聚烯烃，然后将改性的聚烯烃混入未改性的聚烯烃，以调节接枝率，因为这种方法可以适当调节组合物中接枝单体的量。然而，也可先将聚烯烃与预定量的接枝单体混合。
就聚乙烯和乙烯/a-烯烃共聚物而言，可以使用熔体改性方法或溶液改性方法。然而，对聚丙烯而言，从接枝反应的效率和抑制分子量的降低观点来看，溶液改性方法是合乎需要的。
组分(a)的含量为50-90重量份，最好为50-80重量份；组分(b)的含量为10-50重量份，最好为20-50重量份，以上均以这些组分的总重量为基准。
含组分(a)和组分(b)的本发明组合物的熔体流动速率(ASTM,D1238,230℃)为0.5-30克/10分钟，最好为1-10克/10分钟。
本发明的粘性聚丙烯树脂组合物对聚烯烃树脂如聚丙烯树脂、聚酰胺树脂和乙烯/乙烯醇共聚物具有极好的粘合力。
因此，本发明提供一种包括按上述次序层压的聚烯烃层如聚丙烯层、粘合层、和聚酰胺树脂和/或乙烯/乙烯醇共聚物层的多层层合体。粘合层含有本发明的粘性聚丙烯树脂组合物。
本发明的多层层合体至少有三层，第一层的聚烯烃层(A)，第二层是粘合层(B)，第三层是聚酰胺树脂和/或乙烯/乙烯醇共聚物层(C)。这些层按如下组合方式，即A/B/C,A/B/C/B,A/B/C/B/A等进行层压。
聚烯烃层(第一层)一般是聚丙烯树脂层。构成这一层的聚丙烯树脂可以聚丙烯均聚物或丙烯含量不少于93摩尔％的丙烯和其它α-烯烃的共聚物。所述的其它α-烯烃可以是乙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯或1-癸烯。
本发明多层层合体中的粘合层(第二层)含有上述的本发明粘性聚丙烯树脂组合物。
本发明多层层合体中的第三层含有聚酰胺树脂和/或乙烯/乙烯醇共聚物。
聚酰胺树脂的优选例子包括尼龙6、尼龙66、尼龙610、尼龙12、尼龙11、MXD尼龙、无定形尼龙、及对苯二甲酸/己二酸/己二胺共聚物。
另外，乙烯/乙烯醇共聚物中的乙烯含量最好为20-50摩尔％。
乙烯/乙烯醇共聚物是通过皂化乙烯/乙酸乙烯酯共聚物制得的。
本发明的多层层合体是层压熔融态的聚丙烯层、粘合层、和聚酰胺树脂和/或乙烯/乙烯醇共聚物层制得的。
多层层合体例如可用共挤压模塑法、平挤薄膜法、吹胀薄膜法、拉幅双轴向拉伸法或管形双轴向拉伸法制得。
通常在拉伸温度为70-130℃、拉伸比(纵向×横向)为2×2-5×5的拉伸条件下制得收缩薄膜。所得薄膜的厚度为10-200微米。
模塑后，本发明的多层层合体可以在未拉伸状态使用，或模塑后至少在单轴向或最好双轴向拉伸状态下使用。当第三层是聚酰胺树脂层时，多层层合体宜在拉伸后使用。当第三层是乙烯/乙烯醇共聚物层时，多层层合体可在未拉伸或拉伸情况下使用。拉伸提供了较高的强度。因此，当需要高强度时，多层层合体宜在拉伸后使用。然后，当被拉伸时，粘合层的粘合力一般稍有降低。
即使当本发明的多层层合体被拉伸时，粘合力也没有减少很多，而仍保持了足够可用的粘合力。单轴向拉伸时，拉伸比宜在1.5-6倍之间。双轴向拉伸时，拉伸比宜在1.5-6倍之间。
当本发明多层层合体用T-模成型法铸塑时，应以较高的速度进行模塑，如不低于20米/分，最好为20-150米/分，以便获得薄膜强度和粘合力与上述拉伸层合体相同的多层层合体。
本发明的多层层合体具有极高的强度、耐热性和阻气性。另外，可赋予收缩性，使它适于包装肉类如火腿等。
实施例
以下参照实施例对本发明作进一步的描述，但这些实施例对本发明没有限制作用。
在包括如下实施例的本发明中，接枝改性聚丙烯(a)或接枝改性聚烯烃(b)的接枝率是按如下方法测到的接枝率，即用红外光谱仪测量1792cm-1或1860cm-1处的吸光度和4335cm-1处的吸光度，寻找(1792cm-1或1860cm-1处测得的吸光度/4335cm-1处测得的吸光度)并获得由该比值制得的校准曲线图。
实施例1
将85重量份的丙烯/乙烯无规共聚物(r-PP，乙烯含量为3.6摩尔％，熔点为139℃，MFR(230℃)=6克/10分)、5重量份马来酸酐接枝改性的聚丙烯(用3重量％马来酸酐接枝的MAH-PP，在135℃癸烷溶液中极限粘度[η］为0.4 dl/g，熔点为160℃)、和10重量份马来酸酐接枝改性的乙烯/丁烯共聚物(用V型催化剂制得的MAH-EBR，丁烯含量为10摩尔％，用0.5重量％马来酸酐接枝，MFR(190℃)=5克/10分，熔点为70℃)在汉歇尔混合机中进行混合，在单轴挤塑机(加热到230℃，特定的杜尔麦基式螺杆)中进行熔融捏和，以便得到改性的聚丙烯树脂组合物。按下述方法测量这种组合物对乙烯/乙烯醇共聚物和对聚酰胺树脂的粘合强度。
(Ⅰ)测量对乙烯/乙烯醇共聚物的粘合强度的方法。
用乙烯/乙烯醇共聚物(EVOH，商品名为Eval EP-E105,Kurare公司生产，MFR为5.5克/分，乙烯含量为44摩尔％)、上述的改性聚丙烯树脂组合物和上述的r-PP在如下条件下模塑三层平挤薄膜。
膜层构造：
EVOH(外层)/组合物(中间层)/r-PP=40/40/160E
(Ⅱ)测量对聚酰胺树脂粘合强度的方法：
用聚酰胺树脂(PA，商品名为Amilan,Toray有限公司生产)、上述的改性聚丙烯树脂组合物和上述的r-PP在如下条件下模塑三层平挤薄膜。
膜层构造：
PA(外层)/组合物(中间层)/r-PP=40/40/160μ
用双轴挤塑机(Toyo Seiki公司制造)将(Ⅰ)和(Ⅱ)中所得的三层薄膜在80℃加热10分钟，然后在此温度下同时进行双轴向拉伸(纵向拉伸3倍，横向拉伸3倍)，制备三层拉伸薄膜。室温下冷却后，用剥离速度为300毫米/分的T型剥离法测量三层拉伸薄膜的EVOH层或PA层与组合物间界面上的粘合强度。
测量结果列于表1。
实施例2和3
将实施例1中的改性聚丙烯树脂组合物与75重量份(实施例2)或65重量份(实施例3)的丙烯/乙烯无规共聚物(r-PP)混合，并与20重量份(实施例2)或30重量份(实施例3)的马来酸酐接枝改性的乙烯/丁烯共聚物(MAH-EBR)混合。在其它方面按与实施例1相同的方法进行操作，制备改性的聚丙烯树脂组合物，并按实施例1相同的方法测量其粘合强度。
结果列于表1中。
实施例4
除了用马来酸酐接枝改性的乙烯/丙烯共聚物(MAH-EPR，用V型催化剂生产，丙烯含量为20摩尔％，用0.5重量％马来酸酐接枝，MFR(190℃)为3克/10分，熔点为40℃)代替实施例2中使用的MAH-EBR以外，按实施例2相同的方法进行操作。
结果列于表1。
实施例5
除用马来酸酐接枝改性的乙烯/辛烯共聚物(MAH-EOR，用Zr型催化剂制备，辛烯含量为15摩尔％，用0.5重量％马来酸酐接枝，MFR(190℃)为3克/10分，熔点为55℃)代替实施例2中使用的MAH-EBR以外，按实施例2相同的方法进行操作。
结果列于表1。
实施例6
除用丙烯均聚物(h-PP，熔点为165℃,MFR(230℃)=6克/10分)代替实施例3中使用的r-PP以外，按实施例3相同的方法进行操作。
结果列于表1中。
实施例7
除用10重量份马来酸酐接枝改性的聚乙烯(MAH-PE,0.92克/厘米3，用Ti型催化剂制备，用1.0重量％马来酸酐接枝，MFR(190℃)为0.5克/10分，熔点为122℃)和20重量份未改性的乙烯/丙烯共聚物(EPR，用V型催化剂制备，丙烯含量为20摩尔％，MFR(190℃)为3克/10分，熔点为40℃)代替实施例3中使用的30重量份MAH-EBR以外，按实施例3中相同的方法进行操作。
结果列于表1。
实施例8
除用15重量份实施例3中使用的MAH-EBR和15重量份实施例7中使用的EPR代替30重量份实施例3中使用的MAH-EBR以外，按实施例3相同的方法进行操作。
结果列于表1中。
                        表1    (单位为重量份)
 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  实施例8
r-PP    85    75    65    75    75     -    65    65
h-PP     -     -     -     -     -    65     -     -
MAH-PP     5     5     5     5     5     5     5     5
MAH-PE     -     -     -     -     -     -    10     -
MAH-EPR     -     -     -    20     -     -     -     -
MAH-EBR    10    20    30     -     -    30     -    15
MAH-EOR     -     -     -     -    20     -     -     -
EPR     -     -     -     -     -     -    20    15
粘合力，克/15毫米
对EtOH层    140    200    320    160    180    260    190    230
对PA层    100    200    280    210    200    240    100    220
对比例1
除按表2所示的比率使用实施例1中所用的r-PP和MAH-PP，且不用MAH-EBR以外，按实施例1相同的方法进行操作。
结果列于表2中。对比例2和3
除按表2所示的量(重量份)使用实施例1所用的r-PP和MAH-PP，且不用实施例1中所用的10重量份MAH-EBR，而使用20重量份(对比例2)或30重量份(对比例3)实施例7中所用的EPR(未改性的乙烯/丙烯共聚物)以外，按实施例1相同的方法进行操作。
结果列于表2中。
                                表2    (单位为重量份)
    对比例1    对比例2    对比例3
r-PP      95      75      65
h-PP       -       -       -
MAH-PP       5       5       5
MAH-PE       -       -       -
MAH-EPR       -       -       -
MAH-EBR       -       -       -
MAH-EOR       -       -       -
EPR       -      20      30
粘合力，克/15毫米
对EtOH层      10      25      35
对PA层      30      40      60

Claims (7)

1．一种粘性聚丙烯树脂组合物，它包括：
(a)50-90重量份改性聚丙烯或含上述改性聚丙烯的组合物，上述改性聚丙烯用至少一种选自不饱和羧酸和该不饱和羧酸的酸酐的单体接枝改性；和
(b)10-50重量份接枝改性的乙烯/a-烯烃共聚物，上述接枝改性的乙烯/a-烯烃共聚物用至少一种选自不饱和羧酸和该不饱和羧酸的酸酐的单体接枝改性；组分(a)和(b)的总量为100重量份；
其中所述的接枝改性的乙烯/a-烯烃共聚物(b)含有70-95％摩尔乙烯作为该共聚物的构成单元，且具有如下性质：
(ⅰ)密度为0.860-0.930克/厘米3，
(ⅱ)在190℃和2.16公斤负载下的熔体流动速率为0.1-50克/10分钟，
(ⅲ)按改性共聚物(b)的原料共聚物计算的接枝率为0.01-5重量％。
2．一种至少有三个叠合层的多层层合体，它包括：
(ⅰ)聚烯烃层；
(ⅱ)粘性聚丙烯树脂组合物层；及
(ⅲ)聚酰胺树脂和/或乙烯/乙烯醇共聚物层，
所述的层按(ⅰ)、(ⅱ)和(ⅲ)次序进行层压，层(ⅱ)的粘性聚丙烯树脂组合物含有：
(a)50-90重量份改性聚丙烯或含上述改性聚丙烯的组合物，上述改性聚丙烯用至少一种选自不饱和羧酸和该不饱和羧酸的酸酐的单体接枝改性；和
(b)10-50重量份接枝改性的乙烯/a-烯烃共聚物，上述接枝改性的乙烯/a-烯烃共聚物用至少一种选自不饱和羧酸和该不饱和羧酸的酸酐的单体接枝改性；组分(a)和(b)的总量为100重量份；
其中所述的接枝改性的乙烯/a-烯烃共聚物(b)含有70-95％摩尔乙烯作为该共聚物的构成单元，且具有如下性质：
(ⅰ)密度为0.860-0.930克/厘米3，
(ⅱ)在190℃和2.16公斤负载下的熔体流动速率为0.1-50克/10分钟，
(ⅲ)按改性共聚物(b)的原料共聚物计算的接枝率为0.01-5重量％。
3．如权利要求2所述的多层层合体，其特征在于该层合体至少在一个轴向上被拉伸。
4．如权利要求3所述的多层层合体，其特征在于该层合体至少在一个轴向上以原尺寸1.5-6倍的拉伸比被拉伸。
5．如权利要求3所述的多层层合体，其特征在于该层合体被双轴向拉伸。
6．如权利要求5所述的多层层合体，其特征在于该层合体以原尺寸1.5-6倍的拉伸比被双轴向拉伸。
7．如权利要求2所述的多层层合体，其特征在于该层合体是用管状吹塑法制得的双轴取向膜。
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EP0758675B1 (en) 2001-01-31
CA2183301A1 (en) 1997-02-16
DE69611708D1 (de) 2001-03-08
CN1143095A (zh) 1997-02-19
US5695838A (en) 1997-12-09
DE69611708T2 (de) 2001-09-27
EP0758675A3 (en) 1998-07-15
KR100439292B1 (ko) 2004-11-06
EP0758675A2 (en) 1997-02-19
KR970010862A (ko) 1997-03-27

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