CN113603916A - 一种可回收可降解的离型材料及其制备方法 - Google Patents
一种可回收可降解的离型材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种可回收可降解的离型材料及其制备方法,属于离型材料技术领域。本发明所述离型材料,包括基材层和设置在所述基材层上的离型剂涂层,还包括设置于所述基材层和离型剂涂层之间的生物基底涂层;所述基材层为薄膜基材料层或纸质基材料层;所述纸质基材料层包括生物基原纸和薄膜基材料;所述生物基底涂层为丙烯酸酯。所述丙烯酸酯原料组分为SARBIO@5201、SARBIO@5400、SARBIO@6100和184引发剂,所述薄膜基材料的的原料组分为聚乳酸树脂、聚碳酸丁二酯、抗氧化剂和无机填料;所述生物基原纸原料组分为糊化淀粉胶和纸粉。本发明制备的离型材料可回收、减少浪费,符合绿色环保发展的理念。
Description
技术领域
本发明涉及离型材料技术领域,尤其涉及一种可回收可降解的离型材料及其制备方法。
背景技术
当前,生态环境和环境污染问题已引起世界各国的高度重视,我国提出“二氧化碳排放力争于2030年前达到峰值,努力争取2060年前实现碳中和”,为降低碳排放,绿色环保,绿色设计观念应允而生。在消费电子市场,电子产品保护及粘结领域会应用到大量的离型材料,这些离型材料在模切后会直接废弃。普通离型材料主要是以PET、PP、PE等塑料薄膜为基材,这些离型材料在废弃后,导致垃圾处理问题越来越严重。同时若采用常规纸基材料,作为离型材料由于原纸比价粗糙需要双面淋膜PE薄膜层,在使用后也是不可回收或不可降解的,同样会带来大量废弃物和污染。但是随着塑料垃圾处理问题越来越严重,化工行业绿色设计产品越来越受到重视。据此“环保可回收、绿色可降解”的生物降解纸质材料及薄膜材料正响应了目前时代的需求,生物降解材料可以用废弃的材料来加工,符合绿色环保的概念。
中国发明专利CN105860142A公开了一种环保可回收可降解纸制材料及其制备方法,采用糊化淀粉胶和纸粉来制备环保可回收可降解纸质材料,但是纸质材料表面粗糙,不平整,不耐高温,不适宜做离型涂硅处理。中国发明专利CN109135222A公开了一种聚乳酸可降解薄膜及其制备方法,但是其外观晶点缺陷多、光学参数透过率低、雾度高,尤其耐温性差,在高温80℃以上会出现收缩变形,不适宜做高温离型涂硅处理。
发明内容
为解决上述技术问题,本发明提供了一种可回收可降解的离型材料及其制备方法,本发明所述的离型材料可回收、减少浪费,符合绿色环保发展的理念。
本发明的第一个目的是提供一种离型材料,包括基材层和设置在所述基材层上的离型剂涂层,还包括设置于所述基材层和离型剂涂层之间的生物基底涂层;所述基材层为薄膜基材料层或纸质基材料层;所述纸质基材料层包括生物基原纸和薄膜基材料;所述生物基底涂层为丙烯酸酯。
进一步地,所述丙烯酸酯原料组分及其质量百分比为40-50%的SARBIO@5201、20-25%的SARBIO@5400、20-30%的SARBIO@6100和5%的184引发剂。可增强基材强度和耐温性,同时增加和离型剂涂层的附着力。
进一步地,所述薄膜基材料原料组分及其质量百分比为70-75%聚乳酸树脂、10-15%聚碳酸丁二酯、5-10%抗氧化剂和5-10%无机填料。
进一步地,所述抗氧化剂为Irganox 1010(瑞士Ciba公司)、gafos 168(瑞士Ciba公司)和DLTP(德国雅宝)中的一种或多种。抗氧化剂可有效抑制聚合物的热降解和氧化降解。
进一步地,所述无机填料为纳米二氧化硅、纳米二氧化钛、纳米氧化铝和纳米硅酸盐中的一种或多种。无机填料的加入改善聚乳酸的力学性能、耐热性能以及克服材料自身的脆性。
进一步地,所述生物基原纸原料组分及其质量百分比为30-50%糊化淀粉胶和50-70%纸粉。
进一步地,所述糊化淀粉胶原料组分及其质量百分比为25-64%木薯淀粉,5-15%淀粉修饰剂,1-5%增润剂,10-15%增强剂和20-40%聚乙烯醇。
进一步地,所述淀粉修饰剂为聚己内酯。
进一步地,所述增润剂为PCL基聚氨酯预聚体(PCLPU)。
进一步地,所述增强剂为醛基纤维素或聚丙烯酰胺。其中醛基占比成倍增加,有能力和纤维反应生成双倍的共价键,从而更加有效的提高离型材料的强度。
第二个目的是提供离型材料的薄膜基材料层的制备方法,包括如下步骤:
将干燥后的聚乳酸树酯与聚碳酸丁二酯、抗氧化剂、无机填料进行混炼、成型,再经纵向拉伸和横向拉伸得到所述薄膜基材料层。
进一步地,所述纵向拉伸的温度为40-80℃;拉伸的倍数为2.5-3.5倍。
进一步地,所述横向拉伸的温度为50-130℃;拉伸的倍数为2-4倍。
第三个目的是提供离型材料的纸质基材料层的制备方法,包括如下步骤:
(1)木薯淀粉、淀粉修饰剂、增润剂、增强剂、聚乙烯醇加水后搅拌至无颗粒状物,得到糊化淀粉胶;
(2)将步骤(1)所述的糊化淀粉胶和纸粉进行混炼、干燥,得到生物基原纸;
(3)将干燥后的聚乳酸树脂与与聚碳酸丁二酯、抗氧化剂、无机填料进行混炼,得到薄膜基材料;
(4)将步骤(2)所述的生物基原纸两侧淋膜步骤(3)所述的生物基材料,得到纸质基材料层。
第四个目的是提供离型材料的制备方法,包括如下步骤:
将生物基底涂层涂布在基材层(薄膜基材料层或纸质基材料层)上,烘干后贴合离型剂涂层,熟化得到所述离型材料。
本发明的上述技术方案相比现有技术具有以下优点:
(1)本发明所述的丙烯酸酯提高对基材有良好的附着力和高反应性,使理性材料具有更好的强度和耐刮擦性。
(2)本发明的淀粉修饰剂主要是指可降解的聚己内酯大分子,聚己内酯是由植物资源所提取出的原料制备而成,可完全生物降解,是石油基产品有力的替代品。所以热塑性淀粉(TPS)通常用来与聚己内酯(PCL)共混,希望制备出性能良好的淀粉/PCL复合材料。但由于亲水性淀粉和疏水性PCL在热力学上的不相容性。淀粉和PCL通过简单共混获得的产物虽然在一定程度上能表现出良好的机械性能,但是由于淀粉和PCL之间只有氢键作用形成,相对不稳定,而随着淀粉含量的增加,复合材料的机械性能显著下降。本发明所述的增润剂对淀粉或PCL进行化学改性的方法常被用来提高淀粉和PCL之间的相容性和相互作用。增润剂PCL基聚氨酯预聚体(PCLPU)能在淀粉表面形成一种包覆层结构,这个包覆层一方面含有大量的异氰酸酯基团(NCO),能与淀粉中富含的羟基发生反应形成氨酯键,提高淀粉与包覆层之间的相容性;另一方面包覆层中含有的PCL组分与PCL基体通过结晶等物理交联作用产生良好的相容性。所以,综合两方面考虑,PCLPU的加入能明显提高复合材料中淀粉与PCL之间的相互作用和相容性,同时明显提高复合材料的热稳定性和机械性。
(3)本发明所述的糊化淀粉胶是一种可再生的天然生物质高分子化合物,原料来源丰富且价格低廉,是一种可生物降解的再生资源,该种胶黏剂具有无毒、无异味、无公害等特点,同时粘结性能良好。采用糊化淀粉胶和纸粉混合制备的原纸,具有优异的抗张强度和阻隔性能,还可以进行降解处理。
(4)本发明制备的基材层表面平整、光学性能优越;同时采用生物基底涂层处理,增加了薄膜强度,提高基材层耐高温性能,增加和离型剂涂层的附着力,贴合离型剂涂层后不起泡,可制得外观平整的离型材料。本发明所述的离型材料,不仅具有普通离型材料的常规性能,同时具有可回收、减少浪费的优点,符合绿色环保发展的理念。
具体实施方式
下面结合具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1
一种可回收可降解的离型材料及其制备方法,包括以下步骤:
将聚乳酸树酯(PLA)在真空条件下80℃干燥5h,然后将聚乳酸树脂70质量份、聚碳酸丁二酯15质量份、Irganox 1010(瑞士Ciba公司)5质量份、纳米二氧化硅3质量份、纳米二氧化钛7质量份进行混炼,温度170℃,时间3min,将混炼的块料放入双螺杆挤出机进行加工,再经过纵向和横向拉伸即得双向拉伸BOPLA薄膜,主挤出机模头熔融温度220℃;先纵向拉伸时,预热区温度40℃,拉伸区温度60℃,纵向拉伸倍数为2.5倍,冷却至35℃;然后横向拉伸时,预热区温度120℃,拉伸区温度130℃,定型区温度180℃,横向拉伸倍数为2倍,将经热定型后的薄膜经过牵引装置牵引至测厚仪,同时在牵引位置的入口处增加粉尘吸附装置对薄膜进行吸尘处理,然后对薄膜上、下表面进行电晕处理使其表面张力达到38-42mN/m,冷却后得到高强度双向拉伸聚乳酸薄膜。然后再经辊式涂布生物基底涂层,采用高温干燥后贴合有机硅油离型剂涂层,烘干收卷,得到可降解型薄膜基PLA离型材料;其中生物基底涂层包括45质量份SARBIO@5201、20质量份SARBIO@5400、30质量份SARBIO@6100和5质量份184引发剂。
实施例2
一种可回收可降解的离型材料及其制备方法,包括以下步骤:
将聚乳酸树酯(PLA)在真空条件下80℃干燥4h,然后将聚乳酸树脂75质量份、聚碳酸丁二酯10质量份、gafos 168(瑞士Ciba公司)5质量份、纳米二氧化钛10质量份等进行混炼,温度170℃,时间3min,将混炼的块料放入双螺杆挤出机进行加工,再经过纵向和横向拉伸即得双向拉伸BOPLA薄膜,主挤出机模头熔融温度230℃;先纵向拉伸时,预热区温度75℃,拉伸区温度80℃,纵向拉伸倍数为3.5倍,冷却至35℃;然后横向拉伸时,预热区温度120℃,拉伸区温度130℃,定型区温度180℃,横向拉伸倍数为4倍,将经热定型后的薄膜经过牵引装置牵引至测厚仪,同时在牵引位置的入口处增加粉尘吸附装置对薄膜进行吸尘处理,然后对薄膜上、下表面进行火焰处理使其表面张力达到38-42mN/m,冷却后得到高强度双向拉伸聚乳酸薄膜。然后再经狭缝计量挤出涂布生物基底涂层,采用高温干燥后贴合有机硅油离型剂涂层,采用UV照射固化后收卷,得到可降解型薄膜基PLA离型材料;其中生物基底涂层包括40质量份SARBIO@5201、25质量份SARBIO@5400、30质量份SARBIO@6100和5质量份184引发剂。
实施例3
一种可回收可降解的离型材料及其制备方法,包括以下步骤:
各组分的质量份为木薯淀粉50份,淀粉修饰剂10份,增润剂5份,增强剂15份,聚乙烯醇20份;淀粉修饰剂为可降解的聚己内酯,增润剂为PCL基聚氨酯预聚体(PCLPU),增强剂为醛基纤维素;糊化淀粉胶是将各组分按比例添加后搅拌混合形成,然后和纸粉混炼,最后干燥造粒;淋膜聚乳酸树脂75份,聚碳酸丁二酯15份,DLTP(德国雅宝)5份,纳米氧化铝5份,将聚乳酸树脂在80℃下真空干燥5h,然后将干燥的聚乳酸树脂与聚碳酸丁二酯、DLTP(德国雅宝)进行熔融混炼,温度160℃,时间5min;再加入纳米氧化铝进行第二次混炼,混炼时间10min;然后将混炼后的块状料放入双螺杆挤出机进行加工,主挤出机模头熔融温度200℃,淋膜在生物基原纸两面,克重12-20g/m2。然后再经狭缝计量挤出涂布生物基底涂层,采用高温干燥后贴合有机硅油离型剂涂层,采用高温干燥,得到可降解型纸质基离型材料;其中生物基底涂层包括50质量份SARBIO@5201、20质量份SARBIO@5400、25质量份SARBIO@6100和5质量份184引发剂。
实施例4
一种可回收可降解的离型材料及其制备方法,包括以下步骤:
各组分的质量份为木薯淀粉50份,淀粉修饰剂10份,增润剂5份,增强剂15份,聚乙烯醇60份;淀粉修饰剂主要是指可降解的聚己内酯,增润剂PCL基聚氨酯预聚体(PCLPU),增强剂为聚丙烯酰胺;糊化淀粉胶是将各组分按比例添加后搅拌混合形成,然后和纸粉混炼,最后干燥造粒;淋膜聚乳酸树脂75份,聚碳酸丁二酯15份,DLTP(德国雅宝)5份,纳米氧化铝5份,将聚乳酸树脂在80℃下真空干燥5h,然后将干燥的聚乳酸树脂与聚碳酸丁二酯、DLTP(德国雅宝)进行熔融混炼,温度160℃,时间5min;再加入纳米氧化铝进行第二次混炼,混炼时间10min;然后将混炼后的块状料放入双螺杆挤出机进行加工,主挤出机模头熔融温度200℃,淋膜在生物基原纸两面,克重12-20g/m2。然后再经辊式涂布生物基底涂层,采用高温干燥后贴合有机硅油离型剂涂层,采用UV照射固化后收卷,得到可降解型纸质基离型材料。其中生物基底涂层包括48质量份SARBIO@5201、23质量份SARBIO@5400、24质量份SARBIO@6100和5质量份184引发剂。
测试例
对本发明实施例1-4制得的离型材料的相关性能进行测试。
离型材料的厚度按照ASTM D374标准评定。
离型材料的断裂伸长率、抗张强度按照ASTM D882标准评定。
离型材料的润湿张力按照ASTM D2578标准评定。
离型材料的透过率、雾度按照ASTM D1003标准评定。
离型材料的热收缩率按照ASTM D1204标准评定。
表1所示为最终测得离型材料的相关参数:
表1
由表1可知,本发明实施例制备的离型材料,在满足基本需求的同时,具有优异的抗张强度、耐温性,和离型性能,同时采用可降解型基材、减少浪费、重新利用、再循环利用的特点,符合绿色环保发展的理念。
显然,上述实施例仅仅是为清楚地说明所作的举例,并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种离型材料,包括基材层和设置在所述基材层上的离型剂涂层,其特征在于:还包括设置于所述基材层和离型剂涂层之间的生物基底涂层;所述基材层为薄膜基材料层或纸质基材料层;所述纸质基材料层包括生物基原纸和薄膜基材料;所述生物基底涂层为丙烯酸酯。
2.根据权利要求1所述的离型材料,其特征在于:所述丙烯酸酯原料组分及其质量百分比为40-50%的SARBIO@5201、20-25%的SARBIO@5400、20-30%的SARBIO@6100和5%的184引发剂。
3.根据权利要求1所述的离型材料,其特征在于:所述薄膜基材料原料组分及其质量百分比为70-75%聚乳酸树脂、10-15%聚碳酸丁二酯、5-10%抗氧化剂和5-10%无机填料。
4.根据权利要求3所述的离型材料,其特征在于:所述无机填料为纳米二氧化硅、纳米二氧化钛、纳米氧化铝和纳米硅酸盐中的一种或多种。
5.根据权利要求1所述的离型材料,其特征在于:所述生物基原纸原料组分及其质量百分比为30-50%糊化淀粉胶和50-70%纸粉。
6.根据权利要求5所述的离型材料,其特征在于:所述糊化淀粉胶原料组分及其质量百分比为25-64%木薯淀粉,5-15%淀粉修饰剂,1-5%增润剂,10-15%增强剂和20-40%聚乙烯醇。
7.根据权利要求6所述的离型材料,其特征在于:所述增润剂为PCL基聚氨酯预聚体;所述增强剂为醛基纤维素或聚丙烯酰胺。
8.根据权利要求1、3或4所述的离型材料,其特征在于,所述薄膜基材料层的制备方法包括如下步骤:
将干燥后的聚乳酸树酯与聚碳酸丁二酯、抗氧化剂、无机填料进行混炼、成型,再经纵向拉伸和横向拉伸得到所述薄膜基材料层。
9.根据权利要求1、3-7中任一项所述的离型材料,其特征在于,所述纸质基材料层的制备方法包括如下步骤:
(1)木薯淀粉、淀粉修饰剂、增润剂、增强剂、聚乙烯醇加水后搅拌至无颗粒状物,得到糊化淀粉胶;
(2)将步骤(1)所述的糊化淀粉胶和纸粉进行混炼、干燥,得到生物基原纸;
(3)将干燥后的聚乳酸树脂与与聚碳酸丁二酯、抗氧化剂、无机填料进行混炼,得到薄膜基材料;
(4)将步骤(2)所述的生物基原纸两侧淋膜步骤(3)所述的生物基材料,得到纸质基材料层。
10.根据权利要求1-9任一项所述的离型材料的制备方法,其特征在于,包括如下步骤:
将生物基底涂层涂布在基材层上,烘干后贴合离型剂涂层,熟化得到所述离型材料。
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