CN100436122C - 包含气体阻隔层的薄膜 - Google Patents

包含气体阻隔层的薄膜 Download PDF

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CN100436122C
CN100436122C CNB038181193A CN03818119A CN100436122C CN 100436122 C CN100436122 C CN 100436122C CN B038181193 A CNB038181193 A CN B038181193A CN 03818119 A CN03818119 A CN 03818119A CN 100436122 C CN100436122 C CN 100436122C
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polyamide
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CN1671551A (zh
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W·伯尼格
B·杜贾丁
S·詹德罗斯奇
C·施维茨尔
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CFS Kempten GmbH
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Abstract

本发明涉及由至少一层基本上由乙烯/乙烯醇共聚物(EVOH)与至少一种多种聚酰胺的混合物组成的O2气阻隔层制成的单层或多层薄膜、所述薄膜作为包装易腐蚀气产品如食品的用途以及由本发明的薄膜制成的适用于易腐蚀气产物的包装，特别是干酪催熟袋。

Description

包含气体阻隔层的薄膜
技术领域
本发明涉及一种包含至少一层气体阻隔层的塑料薄膜、该薄膜在包装易腐释气产品如食品中的用途以及由该薄膜制成的适用于易腐释气产品如食品的包装，特别是干酪催熟袋，所述气体阻隔层基本上由乙烯/乙烯醇共聚物(EVOH)与至少一种多种聚酰胺的混合物组成。
背景技术
许多易腐产品如食品都包装在塑料薄膜内，目的是防止它们受环境如氧和/或湿气的影响并因此而延长它们的储存期。这类产品有时在储存期间不断释放出气体，因为它们在包装时尚未完全成熟。例如，在干酪催熟期间干酪微生物群形成二氧化碳。因此，用来包装易腐释气产品特别是包装食品的材料必须不仅具有低的氧渗透率，而且还有足够高的二氧化碳渗透率。本文的目的正是要防止这类产品免受外来氧的作用，同时又要使形成的二氧化碳向外释放。形成的CO2从包装内释放到周围避免了二氧化碳在包装内的积聚以及因过高压力引起的包装爆裂。
易腐释气食品也常常含有水份。例如不完全成熟的干酪在用卤水处理后仍然潮湿。因此，适用于这类含可变水份的产品的包装材料应具有氧的不可渗透性或二氧化碳的可渗透性，它们在很大程度上与包装产品或周围的湿含量无关。
近些年来，已开发出许多用于包装易腐释气产品如催熟干酪的塑料薄膜。但是仍然需要满足下列条件的易加工塑料薄膜作包装材料：可能的氧渗透率最低，氧渗透率在很大程度上与环境湿度和/或被包装产品的湿含量无关，而二氧化碳渗透率足够高，在干燥或潮湿状态都是氧渗透率的数倍，从而很可能不仅避免尚在熟化中且因此而释放气体的食品如干酪的腐坏，而且也避免了熟化期间包装爆裂的危险。
发明内容
所以，本发明的目的是提供一种塑料薄膜，它可能的氧渗透率最低，氧渗透率在很大程度上与被包装产品的含湿量和环境湿度无关，同时二氧化碳的渗透率与氧渗透率之比大于或等于3∶1。
按照本发明，达到该目的的方法是制备一种塑料薄膜，它包含至少一层O2气阻隔层，O2气阻隔层基本上由乙烯/乙烯醇共聚物(EVOH)与至少一种多种聚酰胺的混合物组成或由其制成，其中多种聚酰胺由下列3种组分制成
I.聚酰胺6，6
II.聚酰胺6，9和/或聚酰胺6，10和
III.聚酰胺6，I和/或聚酰胺6，T。
用来生产O2气阻隔层的多种聚酰胺的组成如下：
a)15-75mol％组分I，
b)15-55mol％组分II和
c)10-70mol％组分III，
其中各组分加起来的总量必须总是100mol％。
更优选用来生产O2气阻隔层的多种聚酰胺是一种组成如下的多种聚酰胺：
a)50-60mol％组分I，
b)15-55mol％组分II和
c)10-45mol％组分III，
其中各组分加起来的总量必须总是100mol％。
非常优选制造O2气阻隔层的混合物用组成如下的多种聚酰胺生产：
a)35-55mol％组分I，
b)15-55mol％组分II和
c)10-30mol％组分III，
其中各组分加起来的总量必须总是100mol％。
优选基本上构成O2气阻隔层的混合物用包含20-50mol％乙烯，特别优选42-48mol％乙烯，非常优选38-48mol％乙烯的乙烯/乙烯醇共聚物生产，这种共聚物由相应乙烯/醋酸乙烯酯共聚物的皂化获得。
用来生产O2气阻隔层的混合物优选由10-45重量％，特别优选20-40重量％EVOH和55-90重量％或特别优选60-80重量％的上述多种聚酰胺组成，其中这两种组分加起来的总量必须总是100重量％。用来生产该混合物的两种混合物组分优选以传统的混合单元加工成聚合物共混物。
优选按照本发明的薄膜除了O2气阻隔层外，最好还包含至少2个外层或表面层，其中至少一层应该是可热封的。
优选热封层含有选自下列一组用作热封层材料的传统聚合物或混合物：乙烯与醋酸乙烯酯的共聚物，优选醋酸乙烯酯的含量最多为聚合物总量的20重量％；乙烯与α-，β-不饱和羧酸的酯，如丙烯酸丁酯或丙烯酸乙酯的共聚物；乙烯与α-，β-不饱和羧酸，如丙烯酸的共聚物，其中羧酸的含量优选至多为共聚物总重量的15重量％；乙烯与含至少3个碳原子的α-烯烃如丁烯、己烯、辛烯、4-甲基-1-戊烯(LLDPE＝线形低密度聚乙烯)的共聚物，其中共聚物可以从乙烯与α-烯烃用传统催化剂或茂金属催化剂生产以及共聚物的密度应该在0.915-0.93g/cm3范围内。密度≤0.915g/cm3的VLDPE(很低密度PE)更适合于作为热封层材料。优选使用的热封材料是40-65重量％LLDPE与35-60重量％乙烯/醋酸乙烯酯共聚物的混合物，在所有情况下，重量％都相对于100重量％聚合物组分而言。
热封层和第二外层或表面层都可含常用添加剂如防粘剂、抗静电剂和/或润滑剂。第二表面层要用生产热封层所用的聚合物生产，如前所述。特别优选2个外层或表面层由相同的聚合物组分组成，但其中组分可以不同的混合物比例存在。优选第二外层或表面层包含一层由1-25重量％LLDPE与99-75重量％乙烯/醋酸乙烯酯共聚物组成的材料，在所有情况下，重量％都相对于100重量％聚合物组分而言。
因此，按照本发明的薄膜优选具有多层结构，其中除了O2气阻隔层以外，该薄膜还包含2个表面层或外层，其中之一是可热封的，且在所有情况下，2个外层都通过偶联剂层与O2气阻隔层粘接。
优选用于偶联剂层的材料可以是一种基于聚氨酯或聚酯-氨酯或可挤出聚合物的层合胶粘剂。优选用改性聚烯烃作为可挤出偶联剂。优选这种聚合物是一种带羧基的聚烯烃，例如聚乙烯、聚丙烯、乙烯/α-烯烃共聚物或乙烯/醋酸乙烯酯共聚物，在所有情况下它们都接枝上至少一种选自下列一组的单体：α-，β-单不饱和二元羧酸，如马来酸、富马酸、衣康酸或它们的酸酐、酸酯、酸酰胺或酸酰亚胺。还可采用的可挤出偶联剂聚合物是乙烯与α-，β-单不饱和羧酸如丙烯酸、甲基丙烯酸或它们的金属盐如它们的锌盐或钠盐，和/或它们的烷基(C1-C4)酯的共聚物或相应的接枝在聚烯烃上的接枝共聚物，如接枝聚合了所述不饱和酸之一的单体的聚乙烯、聚丙烯或乙烯/α-烯烃共聚物。特别优选将带有接枝α-，β-单不饱和二元羧酸酐的聚烯烃，特别是马来酸酐接枝的乙烯/α-烯烃共聚物或接枝的乙烯/醋酸乙烯酯共聚物与m-LLDPE共混。这种混合物可能包含40-60重量％LLDPE。
至少一层偶联剂层可以着色，优选用已批准食用的着色剂。
按照本发明的O2气阻隔层优选具有至少3μm厚，特别优选4-10μm厚。在所有情况下，任选存在的外层，即表面层的厚度为5-20μm，优选厚8-17μm以及在所有情况下，优选任选地存在的偶联剂层的厚度为5-20μm，优选6-18μm。
按照本发明的单层或多层薄膜可以用任何已知的工艺如薄膜层合、挤出或吹塑工艺生产，优选共挤出吹塑薄膜工艺。
优选薄膜是至少单轴拉伸的，特别优选是双轴拉伸的，其中力图获得纵向与横向上都有一个1∶3的拉伸比。
优选按照本发明的薄膜是可收缩的，特别优选在90-100℃的温度下，纵向收缩率至少为30％，优选至少35％，以及横向收缩率至少35％，优选至少38％。为此按照本发明的薄膜中至少有一层要进行交联，优选通过辐照或电子束固化。
由于本发明的多层薄膜优选包含高含量聚烯烃，优选聚乙烯的外层，它具有低的水蒸气渗透率。
由于氧渗透率与二氧化碳渗透率之比至少为1∶3，且低的氧渗透率是用本发明的薄膜实现的，其中氧渗透率在很大程度上与被包装产品的湿含量和/或环境湿度无关，从而干湿值之比至多为1∶0.9～1∶1.25，优选1∶0.95-1∶1.20，因此，按照本发明的薄膜特别适用于作释气食品的包装材料。
因此本发明也提供按照本发明的薄膜，优选多层薄膜，用来包装易腐释气产品优选食品的用途。按照本发明的薄膜特别适合包装干酪，优选半硬和/或硬干酪，尤其优选仍在催熟中的干酪。
本发明还提供由本发明的薄膜制成的适用于易腐释气产品优选食品，特别优选仍在催熟中的干酪的包装。
因此本发明也提供一种用本发明的薄膜，优选多层薄膜制成的干酪催熟袋。
本发明薄膜的氧渗透率按ASTM D3985确定。为此要在控制条件下将薄膜的一面暴露在氧中并测量氧到达薄膜另一面的输运速率。
薄膜的二氧化碳渗透率类似地按ASTM D3985确定。
氧和二氧化碳渗透率都在不同的环境湿度下测定。
在85％相对湿度下的气体渗透率测量用源自Mocon的Ox-TranTwin仪器进行，而在0％相对湿度下的测量用源自Lissy的L100仪器进行。
由仅用本发明O2气阻隔层中的一种聚合物组分组成的气体阻隔层和一种本发明的O2气阻隔层，在0％和85％相对湿度下的O2和CO2气体渗透率之值，分别如表1A和1B所示。
Figure C0381811900101
具体实施方式
实施例1
一种按照本发明具有以下层结构的薄膜：
a)一个外层，
b)一个偶联剂层，
c)一个O2阻隔层，
d)一个偶联剂层，
e)一个作为外层的热封层，
用共挤出吹塑薄膜工艺生产且在纵向拉伸1∶3.3以及横向拉伸1∶3.5。
薄膜总厚度为55μm。各层的厚度如下：外层a)为10μm，偶联剂层b)为8μm，O2气阻隔层c)为6μm，偶联剂层d)为16μm以及热封层e)为15μm。
各层所用的材料如下：外层a)用56重量％EVA、40重量％LLDPE与4重量％防粘剂的混合物，偶联剂层b)用50重量％马来酸酐改性EVA与50重量％LLDPE的混合物，O2阻隔层c)用乙烯占44mol％的EVOH和多种聚酰胺的混合物，EVOH与多种聚酰胺的重量比为30∶70，偶联剂层d)用50重量％马来酸酐改性EVA与50重量％LLDPE的混合物，热封层e)用78重量％EVA、20重量％LLDPE与2重量％防粘剂与润滑剂的混合物。
按照本发明的薄膜在0％和85％相对湿度下的O2气渗透率值示于表2，其中的测量按上述信息进行。
在85％相对湿度下的气体渗透率测量用源自Mocon的Ox-TranTwin仪器进行，而在0％相对湿度下的测量用源自Lissy的L100仪器进行。
表2：
Figure C0381811900111
多种聚酰胺*＝源自EMS-Chemie AG(瑞士)的聚酰胺BM17SBG

Claims (30)

1.一种包含至少一层O2气阻隔层的薄膜，该阻隔层基本上由一种乙烯/乙烯醇共聚物(EVOH)与至少一种多种聚酰胺的混合物组成，其中多种聚酰胺由3种组分制成
I)聚酰胺66
II)聚酰胺69和/或聚酰胺610和
III)聚酰胺6I和/或聚酰胺6T。
2.按照权利要求1的薄膜，其特征在于多种聚酰胺的组成如下：
a)15-75mol％组分I，
b)15-65mol％组分II和
c)10-70mol％组分III，
其中组分I-III加起来的总量必须总是100mol％。
3.按照权利要求1的薄膜，其特征在于多种聚酰胺的组成如下：
a)15-60mol％组分I，
b)15-55mol％组分II和
c)10-45mol％组分III，
其中组分I-III加起来的总量必须总是100mol％。
4.按照权利要求1的薄膜，其特征在于多种聚酰胺的组成如下：
a)35-55mol％组分I，
b)15-55mol％组分II和
c)10-30mol％组分III，
其中组分I-III加起来的总量必须总是100mol％。
5.按照权利要求1-4中任一项的薄膜，其特征在于所述乙烯/乙烯醇共聚物中乙烯占20-50mol％。
6.按照权利要求5的薄膜，其特征在于所述乙烯/乙烯醇共聚物中乙烯占42-48mol％。
7.按照权利要求5的薄膜，其特征在于所述乙烯/乙烯醇共聚物中乙烯占38-48mo1％。
8.按照权利要求1的薄膜，其特征在于O2气阻隔层由10-45重量％EVOH和55-90重量％多种聚酰胺的混合物组成，在所有情况下，重量％都相对于混合物总量而言。
9.按照权利要求8的薄膜，其特征在于O2气阻隔层由20-40重量％EVOH和60-80重量％多种聚酰胺的混合物组成，在所有情况下，重量％都相对于混合物总量而言。
10.按照权利要求1的薄膜，它包含至少一个外层，其中至少一层是可热封的。
11.按照权利要求10的薄膜，它包含2个外层或表面层，其中至少一层是可热封的。
12.按照权利要求10的薄膜，其特征在于用乙烯/醋酸乙烯酯共聚物(EVA)与LLDPE(线形低密度聚乙烯)的混合物作为外层材料。
13.按照权利要求12的薄膜，其特征在于用40-65重量％乙烯/醋酸乙烯酯共聚物与35-60重量％LLDPE的混合物作为热封层材料，其中聚合物组分加起来的总量必须总是100重量％。
14.按照权利要求1的多层薄膜，其特征在于它由O2气阻隔层和2个外层制成。
15.按照权利要求14的薄膜，其特征在于在所有情况下所述各层靠偶联剂层结合在一起。
16.按照权利要求15的薄膜，其特征在于偶联剂层以马来酸酐接枝的乙烯/醋酸乙烯酯共聚物与LLDPE的混合物为基础。
17.按照权利要求15或16的薄膜，其特征在于至少一层偶联剂层是着色的。
18.按照权利要求1的薄膜，其特征在于该薄膜是单轴拉伸的。
19.按照权利要求1的薄膜，其特征在于该薄膜是双轴拉伸的。
20.按照权利要求1的薄膜，其特征在于该薄膜包含至少一层交联层。
21.按照权利要求1的薄膜，其特征在于该薄膜是可收缩的。
22.按照权利要求1-21中任何一项的薄膜用于包装易腐释气产品的用途。
23.按照权利要求22的用途，用于包装食品。
24.按照权利要求22的用途，用于包装干酪。
25.按照权利要求24的用途，用于包装仍在催熟的干酪。
26.按照权利要求22或权利要求24的用途，用于包装半硬和/或硬干酪。
27.由权利要求1-21中任何一项的薄膜制成的，适用于易腐释气产品的包装。
28.由权利要求1-21中任何一项的薄膜制成的，用于食品的包装。
29.由权利要求1-21中任何一项的薄膜制成的适用于于酪的包装。
30.由权利要求1-21中任何一项的薄膜制成的干酪催熟袋。
CNB038181193A 2002-07-30 2003-07-25 包含气体阻隔层的薄膜 Expired - Fee Related CN100436122C (zh)

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