CN1130367A - 含氧化硅层和聚烯烃层的包装材料 - Google Patents

含氧化硅层和聚烯烃层的包装材料 Download PDF

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CN1130367A
CN1130367A CN95190598A CN95190598A CN1130367A CN 1130367 A CN1130367 A CN 1130367A CN 95190598 A CN95190598 A CN 95190598A CN 95190598 A CN95190598 A CN 95190598A CN 1130367 A CN1130367 A CN 1130367A
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polyolefin
methyl
ethene
film
grafting
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CN1079322C (zh
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P·布里安特
P·托吉曼
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Arkema France SA
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Elf Atochem SA
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Abstract

本发明涉及含有涂覆有氧化硅的膜和聚烯烃膜的材料，配置在氧化硅和聚烯烃膜之间的粘合剂可以选自：
—不饱和烷氧基硅烷接枝的聚烯烃；或
—用不饱和环氧化合物接枝的聚烯烃；或
—乙烯与至少一种不饱和环氧化合物的共聚物。这种材料特别是可用于制造食品包装。

Description

含氧化硅层和聚烯烃层的包装材料
本发明涉及包含氧化硅层和聚烯烃层的包装材料。
更具体地说，它涉及包含涂覆有氧化硅的膜和聚烯烃膜的一种结构，在氧化硅和聚烯烃膜之间配置有粘合剂。例如，就聚烯烃膜而言，可将这种材料热粘合于纸板上，然后用聚乙烯片覆盖这种得到的组合体的每个表面。
这种材料可用于生产液体食品的纸盒形式的包装。
1991年4月25日公开的JP 03 09 98 42(kokai)描述了涂覆有氧化硅的EVOH/乙烯基硅烷膜，在这些膜上用尿烷粘合剂粘上了一层聚丙烯片。
1993年12月14日公开的JP 05 33 05 68(kokai)，描述了涂覆有氧化硅的聚酯膜，在这些膜上用粘合剂粘上了一层乙烯树脂片，这种粘合剂是乙烯-马来酸酐-丙烯酸乙酯共聚物。
现已发现，使用以由硅烷或环氧化合物接枝的聚烯烃为主成分的粘合剂，可得到不能被分层的材料。
本发明是一种包含涂覆有氧化硅的膜和聚烯烃膜的材料，配置在氧化硅和聚烯烃膜之间的粘合剂选自：
-用不饱和烷氧基硅烷接枝的聚烯烃；或
-用不饱和环氧化合物接枝的聚烯烃；或
-乙烯与至少一种不饱和环氧化合物的共聚物。
涂覆有氧化硅的膜在现有技术中是已知的。例如，它可以是聚酯膜，诸如聚对苯二甲酸乙二醇酯(PET)膜、聚对苯二甲酸1，4-丁二醇酯(PBT)膜或聚酰胺(PA)膜。
聚烯烃膜由以下物质制成：聚乙烯、聚丙烯或乙烯共聚物，例如乙烯-丙烯、乙烯-丁烯、乙烯-己烯、乙烯-(甲基)丙烯酸烷基酯或乙烯-醋酸乙烯共聚物等。
就粘合剂而言，用烷氧基硅烷接枝的聚烯烃可选自：
-乙烯或丙烯的均聚物；
-乙烯和醋酸乙烯的共聚物：
-乙烯和至少一种(甲基)丙烯酸烷基酯的共聚物。(甲基)丙烯酸烷基酯中的烷基可最高含10个碳原子，可以是直链、支链或环状。举例来说，(甲基)丙烯酸烷基酯的实例可列举丙烯酸正丁酯、丙烯酸甲酯、丙烯酸异丁酯、丙烯酸2-乙基己酯、丙烯酸环己酯、甲基丙烯酸甲酯或甲基丙烯酸乙酯。在这些(甲基)丙烯酸酯中，优选丙烯酸乙酯、丙烯酸甲酯、丙烯酸正丁酯和甲基丙烯酸甲酯；
-乙烯与α-烯烃诸如丁烯或己烯的共聚物；
-无定形聚α-烯烃(APAO)。所述APAO优选衍生自乙烯、丙烯、丁烯或己烯。可有利的使用丁烯含量高的乙烯-丙烯-丁烯共聚物，或丙烯含量高的乙烯-丙烯-丁烯共聚物，或是丁烯的均聚或共聚物。
可有利地使用乙烯/(甲基)丙烯酸烷基酯的共聚物。
含有不饱和度的烷氧基硅烷可列举
CH2＝CH-Si(OR)3            乙烯基三烷氧基硅烷
CH2＝CH-CH2-Si(OR)3       烯丙基三烷氧基硅烷
CH2＝CR1-CO-O-Y-Si(OR)3   (甲基)丙烯酰氧基烷基三烷氧基硅烷(或(甲基)丙烯酰基硅烷)，其中：
R代表1至5个碳原子的烷基或烷氧基-R2OR3，其中R2和R3是合起来至多有5个碳原子的烷基：
R1代表氢原子或甲基；
Y代表1至5个碳原子的亚烷基。
例如，可使用乙烯基硅烷，诸如三甲氧基乙烯基硅烷、三乙氧基乙烯基硅烷、三丙氧基乙烯基硅烷、三丁氧基乙烯基硅烷、三戊氧基乙烯基硅烷或三(β-甲氧基乙氧基)乙烯基硅烷；烯丙基硅烷，诸如三甲氧基烯丙基硅烷、三乙氧基烯丙基硅烷、三丙氧基烯丙基硅烷、三丁氧基烯丙基硅烷或三戊氧基烯丙基硅烷；丙烯酰基硅烷，诸如丙烯酰氧基甲基三甲氧基硅烷、甲基丙烯酰氧基甲基甲氧基硅烷、丙烯酰氧基乙基三甲氧基硅烷、甲基丙烯酰氧基甲基三甲氧基硅烷、丙烯酰氧基乙基三甲氧基硅烷、甲基丙烯酰氧基乙基三甲氧基硅烷、丙烯酰氧基丙基三甲氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、丙烯酰氧基丁基三甲氧基硅烷、甲基丙烯酰氧基丁基甲氧基硅烷、丙烯酰氧基乙基三乙氧基硅烷、甲基丙烯酰氧基乙基三乙氧基硅烷、甲基丙烯酰氧基乙基三丙氧基硅烷、丙烯酰氧基丙基三丁氧基硅烷或甲基丙烯酰氧基丙基三戊氧基硅烷。
也可使用这些物质的混合物。
优选使用：
CH2＝CH-Si-(OCH3)3            乙烯基三甲氧基硅烷
                                   (VTMO)
CH2＝CH-Si-(OCH2CH3)3        乙烯基三乙氧基硅烷
                                   (VTEO)
CH2＝CH-Si-(OCH2OCH2CH3)3   乙烯基三甲氧基乙氧
                                基硅烷(VTMOEO)，和
CH2＝C(CH3)-CO-O-(CH2)3-Si(OCH3)3
                  3-甲基丙烯酰氧基丙基三甲氧基硅烷。
可在聚烯烃熔融状态、在自由基引发剂存在下进行接枝。
接枝反应可以在单螺杆或双螺杆的挤压机中实现，聚烯烃通过加料漏斗以颗粒状加入挤压机，在挤压机第一个区域通过加热使聚烯烃变成熔融态，然后在第二个区域将反应物加入到熔融态的聚烯烃中。
自由基引发剂可选自过氧化物、过酸、过酸酯或过乙缩醛(peracetal)。通常其用量为被接枝的聚烯烃重量的0.01～0.5％。
例如自由基引发剂可以是：
-过氧化二枯基(DICUP)；
-2，5-二甲基-2，5-二(叔丁基过氧)己烷(DHBP)；
-α，α′-(二叔丁基过氧异丙基)苯(Y1490)。
在使用例如计量泵将自由基引发剂加入到熔融态的聚烯烃中以前，优选将其溶解于液态的乙烯基烷氧基硅烷中。
优选反应物加入区域应足够长，温度应足够低，以保证反应物能良好地分散，以及自由基引发剂尽可能最少地热分解。
接枝反应适宜地在挤压机中处于能使自由基引发剂完全分解的温度下的第三个区域中发生。在挤压机头部熔融物质出口之前，设立一个脱气区，来自引发剂和未反应的乙烯基硅烷的分解产物，例如在真空下于其中脱气。
经冷空气冷却后，接枝的聚烯烃在挤压机的出口例如以粒状回收。
接枝聚合物中的接枝部分的重量比率通常在0.1％到5％之间，最好为0.15～2.5％。
用不饱和环氧化合物接枝的聚烯烃可以选自用不饱和烷氧基硅烷接枝的那类聚烯烃。可有利地采用乙烯/(甲基)丙烯酸烷基酯共聚物。
不饱和环氧化合物具体实例可列举缩水甘油基酯和醚、缩水甘油基衣康酸酯、乙烯基缩水甘油基醚、烯丙基缩水甘油基醚或乙烯基环己烯一氧化物。
还可列举缩水甘油基脂环酯或醚，诸如2-环己烯-1-基-缩水甘油基醚、二缩水甘油基环己烯-4，5-二甲酸酯、缩水甘油基环己烯-4-甲酸酯、缩水甘油基2-甲基-5-降冰片烯-2-甲酸酯和二缩水甘油基桥-顺式-二环[2.2.1]庚-5-烯-2，3-二甲酸酯。
在这些不饱和环氧化合物中，特别优选丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。
可以用接枝不饱和烷氧基硅烷的相同方法将不饱和环氧化合物接枝到聚烯烃上。
至于第三类粘合剂，即乙烯与至少一种不饱和环氧化合物的共聚物，环氧化合物可选自已提及的用于用不饱和环氧化物接枝的聚烯烃粘合剂中的那一类。这种乙烯与至少一种不饱和环氧化合物的共聚物也包括(甲基)丙烯酸烷基酯或醋酸乙烯。(甲基)丙烯酸烷基酯可以选自前述用作用不饱和烷氧基硅烷接枝的聚烯烃的任选共聚单体。举例来说，前述乙烯与至少一种不饱和环氧化合物的共聚物可以列举乙烯、(甲基)丙烯酸烷基酯和甲基丙烯酸缩水甘油酯的共聚物，其中含有2～10％重量，最好是6～8％重量的甲基丙烯酸缩水甘油酯和至少50％的乙烯。
实施例1
准备两个涂有氧化硅的PET膜制的筒，作为筒1和筒2。用等离子法沉积上的氧化硅层厚度为200，PET层厚12μm。
准备不同的粘合剂，用共挤压法或热封法贴至筒1和2的膜上。
粘合剂的组成为：
a.含有29％丙烯酸甲酯的乙烯-丙烯酸甲酯共聚物，在190℃2.16kg载荷下的熔融指数为3dg/分钟；
b.含有3％马来酸酐和15％丙烯酸酯的乙烯-丙烯酸丁酯-马来酸酐共聚物，熔融指数为5dg/分钟；
c.与a相同的乙烯-丙烯酸甲酯共聚物，接枝有0.45％重量的乙烯基三甲氧基硅烷。
对粘合剂/涂有氧化硅的PET膜复合物的剥离力进行测定。
结果总结于以下表1。
                表1
                                      180℃下的剥离力N/20mm                N/25mm                N/25mm
    粘合剂 共挤复合物粘合剂厚度：10μm...     热封复合物粘合剂厚度：350μm     热封复合物粘合剂厚度：20μm
     a乙烯/丙烯酸酯     筒...     筒1     筒2     筒1     筒2
- ＜0.5 1 ＜0.1 ＜0.3
     b乙烯/丙烯酸酯/马来酸酐 1.4 3 - 1 to 2 1 to 2
     c乙烯/硅烷接枝的丙烯酸酯 - 5 18* 5 7*
PET膜撕裂
实施例2
准备与粘合剂a组成相同但乙烯基三甲氧基硅烷接枝度不同的乙烯/丙烯酸甲酯粘合剂。接枝度以接枝部分与接枝的聚合物的相对重量表示。
粘合剂/涂覆氧化硅的PET膜的复合物通过热封法获得。
粘合剂膜厚度为350μm。
剥离力经过测定，结果如表2所示。
               表2
接枝的硅烷的程度  0     0.06     0.1  0.2  0.25  0.3    0.45
剥离力N/25mm180℃ ＜0.5 0.5 1.8 3.5 3.3 4.5 5

Claims (5)

1.含有涂覆有氧化硅的膜和聚烯烃膜的材料，在氧化硅和聚烯烃膜之间配置有的粘合剂选自以下物质：
-用不饱和烷氧基硅烷接枝的聚烯烃；或
-用不饱和环氧化合物接枝的聚烯烃；或
-乙烯与至少一种不饱和环氧化合物的共聚物。
2.按权利要求1的材料，其特征在于粘合剂是接枝了乙烯基三烷氧基硅烷、烯丙基三烷氧基硅烷或(甲基)丙烯酰氧基烷基三烷氧基硅烷的乙烯/(甲基)丙烯酸烷基酯共聚物。
3.按权利要求1或2的材料，其特征在于涂覆有氧化硅的膜由聚对苯二甲酸乙二醇酯制得，而聚烯烃膜由聚乙烯制得。
4.按权利要求1～3之一的材料，其特征在于粘合剂是接枝了(甲基)丙烯酸缩水甘油酯的乙烯-(甲基)丙烯酸烷基酯共聚物。
5.按权利要求1～3的材料，其特征在于粘合剂是乙烯-(甲基)丙烯酸烷基酯-(甲基)丙烯酸缩水甘油酯共聚物。
CN95190598A 1994-06-30 1995-06-28 含氧化硅层和聚烯烃层的包装材料 Expired - Fee Related CN1079322C (zh)

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