CN1058788A - 具有淀粉基质和低渗透性的叠层薄膜及其制备方法 - Google Patents

具有淀粉基质和低渗透性的叠层薄膜及其制备方法 Download PDF

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CN1058788A
CN1058788A CN91105531A CN91105531A CN1058788A CN 1058788 A CN1058788 A CN 1058788A CN 91105531 A CN91105531 A CN 91105531A CN 91105531 A CN91105531 A CN 91105531A CN 1058788 A CN1058788 A CN 1058788A
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laminate film
xylylene
ethylene
starch
described laminate
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C·巴斯蒂奥利
V·贝洛蒂
G·罗曼诺
M·托辛
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Abstract

一种叠层薄膜，包括至少一层聚合材料和一层与 其粘合的疏水材料，该聚合材料层由分解淀粉和烯烃 共聚物组成，具有淀粉基质，不溶于水或至多在水中 膨胀。该薄膜可用于包装食品和制造粪便器，是防气 体和蒸汽的一种非常有效的薄膜。

Description

本发明一般涉及以淀粉物质为基质的生物降解薄膜，具体涉及基本上不溶于水并且适宜于在至少一定时间内形成防液体、气体和蒸汽的有效隔离层、同时在使用后能迅速生物降解的薄膜。
EP-A-0327505号专利介绍了以分解淀粉为基质的聚合材料和合成热塑性聚合材料，这些材料尤其可用于制备模制件，其经受水份后，与相应的仅由淀粉制成的制品相比，具有更佳的尺寸稳定性。
更具体地说，关于薄膜的制备，从EP-A-0032802号专利已知由包括淀粉物质和乙烯-丙烯酸共聚物的组合物可形成具有生物降解挠性的自载薄膜。
本申请人的欧洲专利90011070.1号介绍了由包括淀粉物质和乙烯-乙烯醇共聚物的组合物形成的生物降解薄膜。
上述薄膜在存在水的条件下，具有良好的抗撕裂和防分解的性能，因此能广泛用于取代不能被生物降解的常规合成塑料。但是，在存在水的条件下，上述薄膜会趋于膨胀，用作气体和蒸汽的隔离层时，其性能受到严重损害。然而在某些方面的应用而言，这些性能却是十分重要的。
业已发现，具有上述类型的淀粉物质的薄膜可用疏水物质涂层，形成有效的隔离层，并且淀粉基质层与疏水物质层之间具有良好的互粘性。因此能够制成适合各种用途的叠层薄膜，其中用作防气体和液体的有效隔离层具有十分重要的意义。
本发明的第一个目的在于提供一种叠层薄膜，其特征在于包括至少一层聚合物质和一层与其粘合的疏水物质，而聚合物质层具有淀粉基质并且基本上不溶于水或在水中至多膨胀而已。
具有淀粉基质并且基本不溶于水但至多在水中膨胀的聚合材料意指每100g该种材料能够吸收不超过40g的水，而且在室温下不发生分解。
适宜于用作第一层淀粉基质的物质包括：在水或高沸点增塑剂的存下和适宜于产生能够被加工为热塑性物质的均匀熔体的压力和温度的条件下，通过淀粉和合成热塑性聚合物的熔融得到的聚合掺合物。
合成聚合组份包括：至少一种乙烯化非饱和单体的聚合物或共聚物和具有至少一个极性基团（例如羟基，烷氧基，羧基，羧基烷基，烷基羧基和乙缩醛）的重复单元的聚合物或共聚物。
优选的聚合组份包括：聚乙烯醇和选自乙烯、丙烯、异丁烯和苯乙烯的烯烃与丙烯酸、乙烯醇和/或乙酸乙烯酯及其混合物的共聚物。
优选的合成聚合物是：选自乙烯-乙烯醇、乙烯-丙烯酸、乙烯-乙酸乙烯酯的乙烯共聚物，能够例如通过部份水解乙烯-乙酸乙烯酯产生的乙烯-乙酸乙烯酯和乙烯醇的三元共聚物，以及通过由氧基或烷基羰基部份取代醇官能团进行改性的乙烯-乙烯醇共聚物。
优选的乙烯-乙烯醇共聚物含有10-90%（重量）、较好为10-40%（重量）（15-50%摩尔）、最好为30-45%（摩尔）量的熔体流动指数为2-50、优选6-20的乙烯（210℃，2.16kg）。聚合物的其他优选特征为：
特性粘度（30℃时于二甲基亚砜中）  0.50-0.9
优选特性粘度  0.65-0.80
分子量分布Mw/Mn  1.3-4
分子量分布（气相分配色谱法，于四氢呋喃中）
熔点  ＜180℃
优选熔点  160-170℃
水解度  90-99.9%
＊碱水解并用酸滴定残留碱。
为了提高它们的生物降解度，共聚物可通过由氧基或含1-4个碳原子烷基的烷基羰基取代若干醇官能团（优选0.1-5%摩尔）进行改性。这些改性共聚物可采用已知方法由相应的乙烯-乙烯醇共聚物制取。
用于本发明范围的乙烯-乙酸乙烯酯含有的乙酸乙烯酯摩尔量为5-90%，优选12-80%，和经过水解乙酸酯改性的相应共聚物，优选含有5-90%和经过水解的基团。
乙烯-丙烯酸共聚物可以采用EP-A-0032802号专利中所介绍的那些共聚物。
上述共聚物的混合物可以用作第一层的共聚物质。
构成叠层薄膜第一层的薄膜，由于淀粉的特性含水量或分解阶段期间加入的水份，其含水量应低于6%，优选低于2%（均按重量计）（老化前挤压时计算量）。
如果为了形成能在挤压机中加工的熔融物质而已加入水份，则应在薄膜成形的上流即挤压的中间阶段，通过排气降低含水量。
构成第一层的薄膜可以含有1∶9-9∶1、优选1∶4-4∶1分解淀粉和合成聚合物，但是优先使用含高量淀粉的组合物，即其中合成聚合物的含量占合成聚合物和淀粉总含量的20-40%（重量）。
薄膜可以包括高沸点增塑剂（沸点在150℃以上），例如聚乙二醇，乙二醇，丙二醇，丙三醇，聚丙三醇，聚乙二醇山梨醇，甘露醇，和它们的乙酸酯、乙氧酯或丙氧酯衍生物及其混合物。其用量为淀粉量的0.05-100%（重量），优选0.5-30%（重量）。增塑剂可在淀粉分解期间与乙烯-乙烯醇共聚物结合使用，也可用于增加构成第一层的薄膜的特殊性能。
用于构成第一层物质的淀粉的性质并无特殊严格的要求，它们可以是天然淀粉，也可以是经过物理或化学改性过的淀粉，例如乙氧基淀粉、乙酸淀粉、阳离子淀粉、氧化淀粉和交联淀粉等都可使用。
制备构成第一层薄膜的方法在意大利专利IT67691-A/89，67692-A/89，67413-A/89和67666-A/89中已有介绍，其内容作为参考文献结合在本申请的说明书中。
在本发明的一个较佳实施例中，构成第二层的疏水物质主要由聚对亚二甲苯基和/或其取代衍生物的聚合涂层组成，该涂层通过蒸汽相的化学沉积方法沉积在构成第一层的薄膜上。第二层的厚度可在很宽的范围内并根据得到的所需隔离薄膜性质进行变动，优选厚度约为0.01μm-40μm，尤以0.1μm-10μm为佳。
使用聚合的聚对亚二甲苯基涂层的技术属已知技术，例如在EP-A-0302457号专利申请文件中已有介绍，并且引用了特定的疏水性质的基质。
所用的对亚二甲苯基相当于式Ⅰ：
式中X表示C1-C6烷基，C6-C10芳基，C7-C16芳烷基，囟代烷基或囟代芳烷基，乙酰氧基，氨基烷基，芳基氨基，氰基，烷氧基，羟基，硝基，囟原子，磺基，磺酯基，磷基取代基，硫基，烷基亚砜基或氢原子;
n等于0或整数1-4。
由于其在贮藏和运输过程中的反应作用，对实际应用造成了种种很大的困难，所以优选的起始化合物是对亚二甲苯基或（2，2）-对环芳烷以及它们与以上所述的可能取代相一致的衍生物的二聚体。
对亚二甲苯基的二聚体在室温下实际上是结晶固体，并且能很容易贮藏和运输。该二聚体可采用常规方法制备，例如通过热解对亚二甲苯基或由相应的氢氧化对甲苄基三甲铵通过霍夫曼降解方法进行制备。
在真空条件下，通过蒸汽沉积进行聚合涂层时，对亚二甲苯基的二聚体在真空和高于400℃温度的条件下进行高温裂化，得到式（Ⅰ）的反应残基按所用二聚体在产生对亚二甲苯基的均聚物或共聚物的基质表面进行缩合。
少量的其他单体，例如马来酐或氯丁二烯，在含淀粉基质的材料的薄膜表面上聚合，它们可与（2，2）-对环芳烷及其衍生物一起使用。二价的对亚二甲苯基在形成紧密聚合物的第一层的表面上几乎即时缩合和聚合。
二价的反应对亚二甲苯基的蒸汽沉积装置的结构原理属于已知技术，例如在Kirk-Othmer  Encyclopaedia  of  Chemical  Technology，Third  Ed.，Volume  24，Pages  746-747中已有介绍。这种装置包括：蒸发裂解炉，其中装有（2，2）-对环芳烷或其衍生物，该裂解炉与温度保持低于特定的对亚二甲苯基衍生物的缩合温度的沉积室相连接。
上述沉积室很容易改装为适用于本申请的目的，从而能够连续或半连续沉积聚合涂层。
对亚二甲苯基单体的应用适合于最佳使用多种试剂，例如在促进粘合的真空技术方面通常用于沉积的硅氧烷化合物或磷酸衍生物。
优选的对亚二甲苯基单体，例如有氯对亚二甲苯基，二氯对亚二甲苯基，氰对亚二甲苯基，碘对亚二甲苯基，氟对亚二甲苯基，羟甲基对亚二甲苯基，乙基对亚二甲苯基，甲基对亚二甲苯基，氨基甲基对亚二甲苯基，甲酯基对亚二甲苯基，以及它们的衍生物。
在本发明的另一个实施例中，用于第二层的疏水物质是含有游离酸基的聚合物，优选乙烯-丙烯酸共聚物或乙烯-丙烯酸-丙烯酸烷基酯共聚物。
用于含淀粉基质的第一层的聚合物用碱，优选用氢氧化铵使之成盐，因此制备成可溶于水。表面活性剂、乳化蜡、硅石、聚氧乙烯、聚丙烯酸、聚乙烯吡咯烷酮和聚乙烯醇等都可加到溶液中，以增加其湿润淀粉薄膜的能力和降低涂层的粘着性。由此得到的溶液通过类似涂漆或喷涂技术涂在第一层上，经过热处理和足够的时间，以去除液体溶剂和盐化基团，从而产生不溶于水的聚合涂层。
在本发明另一个实施例中，用于第二层的疏水物质是聚羟基链烷酸酯聚合物，尤其是聚羟基丁酸酯，聚羟基丁酸酯/戊酸酯-乳酸均聚物，以及乳酸与乙醇酸的共聚物或与∑-己内酯的共聚物，聚乙烯-乙烯醇共聚物，或聚乙烯-乙酸乙烯酯共聚物。
涂层可采用吹制或浇注方法通过共挤压进行。
上述实施例制备的疏水涂层还具有良好的隔离特性，并且与淀粉基质的粘合良好。
在本发明的另一个实施例中，第二层由聚乙烯吡咯烷酮或聚乙烯吡咯烷酮酯与下列化合物的共聚物构成：丙烯酸丁酯、戊酸丁酯/甲基丙烯酸甲酯（85∶15-15∶85%重量/重量）、甲基丙烯酸二乙氨基甲酯、乙酸乙烯酯、丙烯酸乙烯酯、丙烯酸或丙烯酸聚合物、无机或有机酯、特别是丙烯酸或丙烯酸聚合物的铵盐。
聚乙烯吡咯烷酮与共聚用单体的摩尔比优选5-60%摩尔。
由共聚物的水溶液或乳液得到的涂层经干燥后，可提供不溶于水的薄膜，其与淀粉基质的第一层粘合良好。
本发明叠层薄膜特别适宜于制造粪便器，例如用于结肠造口术患者护理的一种粪便器，在这种情况下，疏水物质层至少在若干小时内能防止逸出令人讨厌的臭味。一般说来，这种叠层薄膜可用于包装含大量水份的食品。
本发明叠层薄膜将参考以下实施例进一步予以说明。
实施例1：第一淀粉层的制备
制备具有下列组份的组合物：
42%（重量）的Globe  03401  Cerestar（注册商标）淀粉，该淀粉未经干燥，特征含水量为11%（重量）;
39%（重量）的乙烯-乙烯醇共聚物，含42%的1摩尔乙烯，特性粘度（二甲亚砜，30℃）0.39，Mw/Mn  3.6，熔点164℃，水解度99.3，熔体流动指数（230℃，2.16kg）20;
12.8%（重量）丙三醇;
3.2%（重量）水;
3%（重量）EAA  5981共聚物（Dow  Chemical）。
各组份由定量供料装置装到Baker  Perkins  MPC/V-30挤压机中，该挤压机装有分成两部份的双螺杆构件，螺杆直径30mm，螺杆长径比（L/D）为10∶1。双螺杆构件与分成三部份的直径30mm、长径比（L/D）8∶1的单螺杆连接。毛细喷咀的直径4.5mm。挤压温度在挤压机的双螺杆部份保持在120-180℃，在单螺杆部分保持在170-140℃范围内。
将得到的挤出物制成颗粒，然后在约160℃下用压缩吹塑法处理，产生出薄膜。
实施例2和3
将实施例1所生产的一片30cm×30cm薄膜置于市售实验用沉积装置的沉积室中，再将0.4g二氯二对亚二甲苯基装入蒸发部份，在0.05mm  Hg压力的真空和220℃温度条件下蒸发。
将二价的氯对亚二甲苯基保持在680℃，然后在两个不同时期的冷却薄膜表面上进行聚合。得到的厚度示于下表：
实施例  涂层厚度（μm）  对水蒸汽的渗透性＊
1  0  1800
2  1.5  102
3  2  43
＊渗透性以g（30μm）/m2（24h）表示（在温度30℃和相对湿度90%条件下测定）。
实施例4
制备10%的乙烯-丙烯酸（20%丙烯酸）的溶液，在氨存在下pH为10。
将10cm×20cm×60cm的实施例1的薄膜样品在上述溶液中浸渍10分钟，然后在室温下干燥2小时。在38℃温度和90%相对湿度下，该薄膜的渗透性为390g（30μm）/m2（24h），未处理过的薄膜则为1800g（3μm）/m2（24h）。
经过处理的薄膜，透明度更高。

Claims (19)

1、一种叠层薄膜，其特征在于该类薄膜包括至少一层具有淀粉基质并且不溶于水或至多在水中膨胀的第一聚合材料层和一层与该聚合材料层相粘合的第二疏水材料层。
2、按权利要求1所述的叠层薄膜，其中聚合材料由包括分解淀粉和合成热塑性聚合物的组合物组成，其中所述合成热塑性聚合物是至少有一种乙烯化非饱和单体的共聚物，所述聚合物具有1个选自羟基、烷氧基、羧基、羧基烷基、烷基羧基和乙缩醛的极性基团的重复单元。
3、按权利要求2所述的叠层薄膜，其中所述聚合物选自聚乙烯醇和选自乙烯、丙烯、异丁烯和苯乙烯的烯烃与丙烯酸、乙烯醇或乙酸乙烯酯的共聚物。
4、按权利要求1所述的叠层薄膜，其中与淀粉基质聚合的材料是由包括分解淀粉和选自乙烯-乙烯醇、经由氧基或烷基羰基取代某些羟基进行改性的乙烯-乙烯醇、乙烯-丙烯酸、乙烯-乙酸乙烯酯、乙烯-乙烯醇-乙酸乙烯酯以及它们的混合物的乙烯共聚物的组合物组成。
5、按权利要求4所述的叠层薄膜，其中乙烯共聚物是乙烯含量为15-50%摩尔、优选30-45%摩尔的乙烯-乙烯醇。
6、按权利要求2所述的叠层薄膜，其特征在于乙烯共聚物包括乙酸乙烯酯摩尔量为12-80%的乙烯-乙酸乙烯酯。
7、按权利要求1所述的叠层薄膜，其中第一层包括淀粉和乙烯共聚物，其重量比为1∶4-4∶1。
8、按权利要求7所述的叠层薄膜，其中构成第一层的聚合材料包括高沸点增塑剂，并且含水量不超过6%（重量）（老化前挤压时计算量）。
9、按权利要求1所述的叠层薄膜，其中第二层是由具有式（Ⅰ）的对亚二甲苯基单体的聚合物或共聚物组成：
Figure 911055312_IMG1
式中X表示C1-C6烷基，C6-C10芳基，C7-C16芳烷基，囟代烷基或囟代芳烷基，乙酰氧基，氨基烷基，芳基氨基，氰基，烷氧基，羟基，硝基，囟原子，磺基，磺酯基，磷基取代基，硫基，烷基亚砜基或氢原子;
n等于0或整数1-4。
10、按权利要求9所述的叠层薄膜，其中对亚二甲苯基单体选自氯对亚二甲苯基，二氯对亚二甲苯基，氰对亚二甲苯基，碘对亚二甲苯基，氟对亚二甲苯基，羟甲基对亚二甲苯基，乙基对亚二甲苯基，甲基对亚二甲苯基，氨基甲基对亚二甲苯基，甲酯基对亚二甲苯基，以及它们的衍生物。
11、按权利要求1所述的叠层薄膜，其中第二层的疏水材料是含游离酸基的聚合物。
12、按权利要求9所述的叠层薄膜，其中含游离酸基的聚合物是乙烯-丙烯酸或乙烯-丙烯酸-丙烯酸烷基酯共聚物。
13、按权利要求1所述的叠层薄膜，其中第二层的疏水材料是聚羟基链烷酸酯聚合物，乳酸均聚物，乳酸与乙醇酸的共聚物或与∑-己内酯的共聚物，聚乙烯-乙烯醇共聚物，或聚乙烯-乙酸乙烯酯共聚物。
14、按权利要求1所述的叠层薄膜，其中第二层包括聚乙烯吡咯烷酮或聚乙烯吡咯烷酮酯与丙烯酸丁酯、戊酸丁酯/甲基丙烯酸甲酯、甲基丙烯酸二乙氨基甲酯、乙酸乙烯酯、丙烯酸乙烯酯、丙烯酸或丙烯酸聚合物、丙烯酸酯或丙烯酸聚合物的酯。
15、由权利要求1所述的叠层薄膜制造的粪便器。
16、权利要求1的叠层薄膜用于包装食品。
17、制备权利要求1所述叠层薄膜的方，其中在真空和蒸汽冷凝条件下，通过对亚二甲苯基或其蒸汽态衍生物的单体反应蒸汽沉积在由淀粉材料薄膜组成的基质上，将疏水材料层涂于含淀粉基质的基质上。
18、按权利要求17所述制备叠层薄膜的方法，包括下列步骤：
用碱、优先用氢氧化铵使含游离酸基的聚合物盐化，生成聚合物水溶液;
将该溶液按薄层方式沉积在淀粉基质层的至少一层表面上。
外热加温一段时，蒸去溶剂，去除聚合物中的碱基，使其不溶于水。
19、按权利要求18所述方，其中将选自表面活性剂、乳化蜡、硅石、多氧基乙烯、聚丙烯酸、聚乙烯吡咯烷酮、聚乙烯醇以及它们的混合物的添加剂加到聚合物水溶液中。
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IT1242722B (it) 1994-05-17
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AU650472B2 (en) 1994-06-23
HU9201192D0 (en) 1992-07-28
DE69129291T2 (de) 1998-11-05
EP0495950B2 (en) 2002-04-03
EP0495950A1 (en) 1992-07-29
JPH05505354A (ja) 1993-08-12
ES2115617T5 (es) 2002-10-16
ES2115617T3 (es) 1998-07-01
AU8311891A (en) 1992-03-02
CA2067396C (en) 2003-01-14
WO1992002363A1 (en) 1992-02-20
EP0495950B1 (en) 1998-04-22
FI921285A0 (fi) 1992-03-25
US5384170A (en) 1995-01-24
DE69129291T3 (de) 2002-08-14
KR920702289A (ko) 1992-09-03
JP2961147B2 (ja) 1999-10-12
HUT61925A (en) 1993-03-29
BR9105849A (pt) 1992-08-25
IL99133A0 (en) 1992-07-15
PL291367A1 (en) 1992-03-09
IT9067634A0 (it) 1990-08-09
IT9067634A1 (it) 1992-02-09
TW252130B (zh) 1995-07-21
ATE165274T1 (de) 1998-05-15
FI921285A (fi) 1992-03-25
DE69129291D1 (de) 1998-05-28

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