CN102492177A - 食品接触用生物基片材及其制备方法 - Google Patents
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Abstract
本发明涉及一种食品接触用生物基片材及其制备方法，其各组分按质量份数计的配比为：淀粉40～70%；增塑改性剂0.5～2%；偶联剂0.5～1%；高密度聚乙烯15～30%；茂金属聚乙烯5～10%；无机填充剂5～20%；润滑剂0.5～1%。所述方法是先将淀粉粉碎后加入增塑改性剂进行改性，接着加入偶联剂、高密度聚乙烯、茂金属聚乙烯、无机填充剂、润滑剂，在加热条件下搅拌，然后冷却物料，经过双螺杆造粒机挤出粒料，再通过锥形双螺杆片材机做出片材。在加热条件下混料，高密度聚乙烯和茂金属聚乙烯颗粒表面部分融熔，粘附了大量粉体材料，减少了加工过程中的粉尘，提高了分散效果，克服了加工过程中的聚集问题。
Description
技术领域
本发明涉及一种食品接触用生物基片材及其制备方法，属于高分子材料技术领域。
背景技术
随着经济的高速发展，人们生活节奏逐步加快，健康意识也大大加强，对卫生一次性食品包装材料的卫生指标要求也更加关切。目前市场上一次性食品接触用塑料大都来自传统不可再生的石油化工产品，也因此造成“白色污染”问题日益严重，各国都在大力推广作为其替代品的安全卫生的生物基塑料。在生物基塑料中，淀粉这种天然高分子物质以来源广泛、价格低廉、再生周期短、能在多种环境下降解等优点，成为研究的重点。
国内外已经开展了几十年关于淀粉基塑料的研究，通过添加多种助剂，淀粉用于包装材料问题已经解决。然而当参照GB18006.1-2009标准对这些淀粉基塑料进行卫生指标检测时，特别是在蒸发残渣实验检测，部分助剂会被溶出，造成“淀粉基塑料一次性餐饮具卫生理化指标”中蒸发残渣检测不达标。CN200810024909.5将淀粉改性后与聚丙烯粉料混合制片材，然后制成餐饮用品，该方法解决了淀粉与聚丙烯相容的问题，但此材料在低温冷藏时，材料的性能下降比较明显； CN200610042002.2将淀粉接枝改性，其配方中用较大比例的低分子醇类和脂类作为增塑剂，而引发剂为过氧化二异丙苯，其毒性为中度；CN201010245875.X也有同样的问题，并且把比例高达6%的白油或聚乙烯蜡作为润滑剂。这些低分子量的醇类、脂类以及白油等均易被蒸发残渣试验中溶出造成卫生指标超标。将淀粉改性以后做成塑料用品或包装制品，在公开的这些文献报道和专利文件内容中没有相关的卫生指标检测报告，从涉及的助剂种类和用量来看，不适合直接应用到食品接触类材料。
发明内容
有鉴于此，本发明的目的在于提供一种食品接触用生物基片材及其制备方法，该方法包括淀粉的改性，包括混料工艺和制作工艺，而且在此工艺条件下生产出来的片材可以直接用于接触食品，满足淀粉基塑料一次性餐饮具卫生理化指标。
为了达到上述目的，本发明提供一种食品接触用生物基片材，所述食品接触用生物基片材各组分按质量份数计的配比为：
淀粉 40-70%；
增塑改性剂 0.5-2%；
偶联剂 0.5-1%；
高密度聚乙烯 15-30%；
茂金属聚乙烯 5-10%；
无机填充剂 5-20%；
润滑剂 0.5-1%。
优选地，其中所述淀粉为玉米淀粉、土豆淀粉、木薯淀粉、红薯淀粉、芋头淀粉或高粱淀粉中的一种。
优选地，其中所述增塑改性剂为十二烯基丁二酸酐、顺丁烯二酸酐、甲基丙烯酸、聚乙二醇、马来酸酐-丙烯酸共聚物、山梨醇或柠檬酸三丁酯中的一种或几种。
优选地，其中所述偶联剂为硅烷偶联剂、铝酸酯类、钛酸酯类或钛复合偶联剂，为提高材料中无机粉体与基础材料改性淀粉和合成高分子材料的界面强度，这些偶联剂可根据所使用的无机粉体种类来选择。
优选地，其中所述高密度聚乙烯的熔融指数不低于0.2g/10min。
优选地，其中所述茂金属聚乙烯购自美国埃克森公司，其产品牌号是1018FA。
优选地，其中所述无机填充剂为食品级的滑石粉、高岭土、白云母或硅藻土粉体，其细度大于200目，优选为大于400目。
优选地，其中所述润滑剂为硬脂酸钙、聚乙烯蜡、氧化聚乙烯蜡、环氧硬脂酸辛酯中的一种或几种。
所述食品接触用生物基片材的制备方法，包括以下步骤：
1）将40-70%的淀粉经粉碎机磨碎细化至800～1200目；
2）将细化好的淀粉加入到高速搅拌机中，再加入0.5～2%的增塑改性剂进行改性，温度设置为80～160℃，搅拌5～30min，加入偶联剂，继续搅拌3～5min；
3）接着加入上述比例的高密度聚乙烯和茂金属聚乙烯、无机填充剂、润滑剂，保持温度与改性时温度一致，搅拌5～20min，此时高密度聚乙烯和茂金属聚乙烯表面已经部分融熔，部分粉体物料粘附在其表面，准备放料；
4）物料出高速搅拌机以后，在冷混锅内搅拌5～10min，待物料冷却到50℃以下；
5）将混好的物料加入双螺杆挤出机，其中，长径比为44:1～52:1，机筒各区温度设置为135℃～200℃、机头温度设置为170℃～180℃，螺杆转速为240～280转/分，挤出造粒；
6）将造粒后的物料加入锥形双螺杆片材机，经过三辊制成所述食品接触用生物基片材，其中，锥形双螺杆片材机中的挤出机料筒温度设置为190℃～215℃，模头温度设置为170℃～190℃，根据片材的用途来设定片材的宽度和厚度。
与现有技术比较，本发明具有以下有益效果：
1）本发明所提供的片材可以通过GB18006.1-2009标准的检测，蒸发残渣和重金属检测全部达标，可直接应用于接触食品；
2）本发明选用的反应型增塑剂对淀粉进行改性，使淀粉的羟基与增塑剂发生反应，从而使淀粉界面可以与高密度聚乙烯和茂金属聚乙烯相容，而融合在一起，在偶联剂的作用下，使有机物成分和无机填充粉末结合在一起；
3）本发明采用茂金属聚乙烯，是通过其高熔融指数来改善片材的力学性能，尤其是低温的韧性；
4）本发明中避免了有机小分子聚合物作为助剂，无机填充剂也是选用食品级的，这些都为本材料满足卫生指标提供了保障；
5）本发明为淀粉高值化利用和制造绿色材料提供了实用化的技术。
具体实施方式
以下将结合具体实施例对本发明作进一步地详细说明。
实施例1
将40kg玉米淀粉经粉碎机磨碎细化至800目；
将细化好的淀粉加入到高速搅拌机中，再加入增塑、改性剂山梨醇1kg和柠檬酸三丁酯1kg，温度设置为100℃，搅拌5min，然后加入偶联剂铝酸酯1kg，高速搅拌3min；
接着向高速搅拌机中一起加入高密度聚乙烯30kg和茂金属聚乙烯 10kg、滑石粉16kg、润滑剂硬脂酸钙1kg，温度保持在100℃，高速搅拌10min，准备放料，此时高密度聚乙烯和茂金属聚乙烯表面已经部分融熔，部分粉体物料粘附在其表面；
物料出高速搅拌机以后，在冷混锅内低速搅拌8min，待物料冷却到40℃左右；
将混好的物料加入双螺杆挤出机，长径比为44:1，机筒各区温度设置范围为140℃～195℃，机头温度设置为175℃，螺杆转速260转/分，挤出造粒；
将造粒后的物料加入锥形双螺杆片材机，经过三辊制成所述食品接触用生物基片材，锥形双螺杆片材机中的挤出机料筒温度设置为190℃、200℃、200℃、200℃、190℃，模头温度设置为185℃、178℃、182℃、178℃、185℃，根据片材的用途来设定片材的宽度为650mm和厚度为0.9mm。
对此片材进行性能检测，结果是：
| 拉伸强度(MPa) | 伸长率(%) | 撕裂强度(KN/m) | |
| 纵向 | 11.76 | 98.21 | 72.11 |
| 横向 | 10.74 | 15.86 | 88.08 |
根据GB18006.1-2009“淀粉基塑料一次性餐饮具卫生理化指标”标准对其进行检测，其蒸发残渣结果是：
各项指标均低于标准要求值，可以直接应用于食品接触。
实施例2～9的制备过程与实施例1相同，区别在于原料比例、加工条件不同，如下表1和表2所示：
表1：
表2：
实施例2～9的制备片材的力学性能检测结果如表3所示：
表3：
实施例2～9的制备片材的蒸发残渣和重金属检测结果如表4所示：
表4：
从以上数据可以看出按照本发明技术方案制备的生物基片材性能良好，可直接用于接触食品。
所应说明的是，以上具体实施方式仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。
Claims (9)
1.一种食品接触用生物基片材，其特征在于，所述食品接触用生物基片材各组分按质量份数计的配比为：淀粉40～70%；增塑改性剂0.5～2%；偶联剂0.5～1%；高密度聚乙烯15～30%；茂金属聚乙烯 5～10%；无机填充剂5～20%；润滑剂0.5～1%。
2.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述淀粉为玉米淀粉、土豆淀粉、木薯淀粉、红薯淀粉、芋头淀粉或高粱淀粉中的一种。
3.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述增塑改性剂为十二烯基丁二酸酐、顺丁烯二酸酐、甲基丙烯酸、聚乙二醇、马来酸酐-丙烯酸共聚物、山梨醇或柠檬酸三丁酯中的一种或几种。
4.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述偶联剂为硅烷偶联剂、铝酸酯类、钛酸酯类或钛复合偶联剂。
5.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述高密度聚乙烯的熔融指数不低于0.2g/10min。
6.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述茂金属聚乙烯购自美国埃克森公司。
7.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述无机填充剂为食品级的滑石粉、高岭土、白云母或硅藻土粉体，其细度大于200目。
8.根据权利要求1所述的食品接触用生物基片材，其特征在于，所述润滑剂为硬脂酸钙、聚乙烯蜡、氧化聚乙烯蜡、环氧硬脂酸辛酯中的一种或几种。
9.一种权利要求1所述的食品接触用生物基片材的制备方法，其特征在于，所述方法包括以下步骤：
1）将40～70%的淀粉经粉碎机磨碎细化至800～1200目；
2）将细化好的淀粉加入到高速搅拌机中，再加入0.5～2%的增塑改性剂进行改性，温度设置为80～160℃，搅拌5～30min，加入偶联剂，继续搅拌3～5min；
3）分别加入上述比例的高密度聚乙烯和茂金属聚乙烯、无机填充剂、润滑剂，保持温度与改性时温度一致，搅拌5～20min，此时高密度聚乙烯和茂金属聚乙烯颗粒表面已经部分融熔，部分粉体物料粘附在其表面，准备放料；
4）物料出高速搅拌机以后，在冷混锅内搅拌5～10min，待物料冷却到50℃以下；
5）将冷却后的物料加入双螺杆挤出机，其中，长径比为44:1～52:1，机筒各区温度设置为135℃～200℃、机头温度设置为170℃～180℃，螺杆转速为240～280转/分，挤出造粒；
6）将造粒后的物料加入锥形双螺杆片材机，经过三辊制成所述食品接触用生物基片材，其中，锥形双螺杆片材机中的挤出机料筒温度设置为190℃～215℃，模头温度设置为170℃～190℃。
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