CN103772802A - 一种用于制造高温蒸煮cpp薄膜的聚丙烯树脂组合物及其高温蒸煮cpp薄膜 - Google Patents
一种用于制造高温蒸煮cpp薄膜的聚丙烯树脂组合物及其高温蒸煮cpp薄膜 Download PDFInfo
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Abstract
本发明公开了一种用于制造高温蒸煮CPP薄膜的聚丙烯树脂组合物和一种高温蒸煮CPP薄膜,包括聚丙烯树脂基料和添加剂,重量比为100∶0.08~0.20,所述的聚丙烯树脂基料,为由93~99.5wt%的丙烯与0.5~7wt%的C4-C8α-直链烯烃共聚而成的聚丙烯共聚物,其熔体流动速率为7.0~10.0g/10min,等规度为95.0~98.0%,所述的添加剂包括主抗氧剂、辅抗氧剂A、辅抗氧剂B、吸酸剂,添加剂的组分配比以重量份计,当主抗氧剂为100份时,辅抗氧剂A为40~55份,辅抗氧剂B为20~35份,吸酸剂为50份。本发明不仅能满足高温蒸煮CPP加工工艺要求,并能保证高温蒸煮CPP薄膜具有更为优良的机械性能、光学性能和抗色变性能。
Description
技术领域
本发明涉及一种聚丙烯树脂组合物,特别涉及用于制造高温蒸煮CPP薄膜的聚丙烯树脂组合物,以及高温蒸煮CPP薄膜。
背景技术
流延薄膜(Castfilnl)是通过熔体流延骤冷生产的一种无拉伸、非定向的平挤薄膜。与吹膜相比,其特点是生产速度快,产量高,薄膜透明性、光泽性、厚度均匀性良好,各向性能平衡性优异。同时,由于是平挤薄膜后续工序如印刷、复合等极为方便,因而广泛的应用于纺织品、鲜花、食品、日用品的包装。
CPP薄膜可分为蒸煮级CPP薄膜(Retort CPP,简称RCPP)和镀铝级CPP薄膜(Metalize CPP,简称MCPP)、通用CPP薄膜(General CPP,简称GCPP)等。蒸煮级是指能与PET、NY、铝箔等通过干式复合后,制成耐高温蒸煮杀菌的复合用基材薄膜。非蒸煮级是指不能做蒸煮袋内层基材,只能用于常规包装的薄膜。蒸煮级CPP膜一般可分为普通蒸煮、中高温蒸煮、高温蒸煮。普通蒸煮耐温121℃以下,中高温蒸煮在121℃~135℃/30分钟,高温蒸煮应耐135℃/30分钟。
相对于普通CPP薄膜,高温蒸煮CPP膜具有特别的性能要求:耐高温、高压,有杰出的热封强度、复合强度。蒸煮后其物理性质也不会下降、不破裂、不漏气,袋内食物不会变质变味。在运输及销售时要求在冷藏中能耐低温、不脆裂。这种新型包装材料的使用,不仅大大延长了食品的保质期,最大限度地保持了食品的新鲜和营养,而且在相当程度上减少了抽真空、高压、压力波动时的破包现象,从而在很大程度上降低了成本,普及了高档方便食品的包装。这一切都对制造高温蒸煮CPP薄膜的原料聚丙烯树脂提出了更高的要求,不仅要保证其具备优良的成膜加工性能,还要使制得的薄膜具有良好的机械性能和光学性能。高温蒸煮CPP薄膜的特性主要取决于聚丙烯树脂基料的特性(如共聚单体含量、等规度、分子量和分子量分布等),但其稳定体系(添加剂配方)也至关重要。因为高温蒸煮CPP薄膜的加工是在高温、长流程的有氧状态下进行,聚合物大分子会发生热氧化降解,从而严重影响薄膜的各项性能。因此,制造高温蒸煮CPP薄膜的原料聚丙烯树脂中必须含有抗氧化的添加剂,当然,添加剂同时还具有提高薄膜在长期使用过程中耐氧化性能的作用。但是添加剂选择不当或者添加剂加入量的不当导致薄膜在获得良好的抗氧化性的同时,将导致薄膜的品质下降,甚至反而使得成膜加工性能变差。目前常见的主抗氧剂四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯,辅助抗氧剂三(2,4-二叔丁基苯基)亚磷酸酯为代表的稳定体系被广泛用于CPP专用料中,但这一配方体系最大的不足之处是在于抗变色能力差,薄膜存放不久易产生变黄、变红等色变现象,影响高温蒸煮CPP薄膜的微外观及性能。因此,CPP专用料中添加剂配方的研究一直备受关注。
发明内容
本发明提供了一种用于制造超高温蒸煮CPP薄膜的聚丙烯树脂组合物的制备方法,它对采用的添加剂进行了改进,所要解决的技术问题是使聚丙烯树脂不仅能满足高温蒸煮CPP薄膜成膜加工的工艺要求,并能保证以此为原料制造的高温蒸煮CPP薄膜具有更为优良的机械性能、光学性能和抗色变性能。
以下是本发明具体的技术方案:
一种用于制造高温蒸煮CPP薄膜的聚丙烯树脂组合物,包括聚丙烯树脂基料和添加剂,聚丙烯树脂基料与添加剂的重量比为100∶0.08~0.20,
所述的聚丙烯树脂基料,根据ASTM D1238测得其熔体流动速率为7.0~10.0g/10min,根据GB/T 2412-2008测得等规度为95.0~98.0%;
所述的添加剂包括主抗氧剂、辅抗氧剂A、辅抗氧剂B、吸酸剂,其中:
主抗氧为1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯(分子式C54H78O3,CAS号:1709-70-2);
辅抗氧剂A为四(2,4-二叔丁基酚)-4,4'-联苯基二亚磷酸酯(又名抗氧化剂THP-EPQ,分子式C68H92O4P2,CAS号:119345-01-6);
辅抗氧剂B为N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺(分子式C24H50N4,CAS号:61260-55-7);
吸酸剂为硬脂酸钙(分子式:C36H70CaO4,CAS号:1592-23-0);
添加剂的组分配比以重量份计,当主抗氧剂为100份时,辅抗氧剂A为40~55份,辅抗氧剂B为20~35份,吸酸剂为50份。
优选地,聚丙烯树脂基料为由93~99.5wt%的丙烯与0.5~7wt%的C4-C8直链α-烯烃共聚而成的聚丙烯共聚物。
优选地,上述添加剂的组分配比以重量份计,当主抗氧剂为100份时,辅抗氧剂A为45~50份,辅抗氧剂B为25~35份。
优选地,上述聚丙烯树脂基料与添加剂的重量比为100∶0.10~0.15。
本发明还提供了一种用于制造高温蒸煮CPP薄膜的聚丙烯树脂组合物的制备方法,包括以下步骤:将上述聚丙烯树脂基料和主抗氧剂、辅抗氧剂A、辅抗氧剂B、吸酸剂分别计量后均匀混合;投入双螺杆挤出机进行熔融混合造粒,其中物料在螺杆内的停留时间为2~4分钟,螺杆温度控制为190~220℃,螺杆转速控制为80~120转/分;将得到的聚丙烯树脂粒子经冷却干燥后即为聚丙烯树脂组合物成品。
本发明还提供了一种高温蒸煮CPP薄膜,其原料为上述聚丙烯树脂组合物。
本发明的关键是对添加剂进行了改进,发明人通过实验发现,所选择的这些抗氧剂以合适的比例配伍,其抗氧作用起着协同的作用,性能大为提高,从而可使添加剂的添加总量得以降低。严格说来,在聚丙烯基料中添加剂也属于一种杂质,在保证抗氧性能的前提下,添加总量的减少显然对成膜加工性的提高、薄膜制品强度的提高和浊度的降低极为有利。因此,与现有技术相比,本发明提供的聚丙烯组合物不仅保证了其具有良好的加工性能,满足高温蒸煮CPP膜的加工工艺要求,且使以此为原料制造的高温蒸煮CPP薄膜具有更为优良的机械性能、光学性能和抗色变性能。
具体实施方式
以下结合实施例对本发明进行详细说明。但应理解,以下实施例仅是对本发明实施方式的举例说明,而非是对本发明的范围限定。
在实施例中,非特别说明,所有原料均为市售。
由于本发明的关键在于添加剂的改进,其它部分与现有技术基本相同,因此实施例将注重添加剂配方及添加量试验数据的列举。
本发明及其实施例中高温蒸煮CPP薄膜的有关数据按以下测试方法获得:
1.薄膜的拉伸断裂强度、断裂标称应变、直角撕裂强度:按GB/T13022-1991测量薄膜的透光率、
2.薄膜的雾度:按GB/T2410测试。
3.薄膜的表面光泽度:按ASTM D2457-08测试。
4.薄膜的热封温度、热封强度:按QBT 2358-1998测试
【实施例1~8】
取粉状聚丙烯树脂基料(为淡乳白色粉料,采购于上海石油化工股份有限公司)500kg,按所需比例加入添加剂的各组分,拌匀。物料投入双螺杆挤出机进行熔融混合造粒,物料在螺杆内的停留时间为2~4分钟,螺杆温度控制为190~220℃,螺杆转速控制为80~120转/分。得到的聚丙烯树脂粒子经冷却干燥后即为成品。每一实施例取500kg样品。
聚丙烯树脂基料为由93~99.5wt%的丙烯与0.5~7wt%的C4-C8α-烯烃共聚而成的聚丙烯共聚物,其熔体流动速率为7.0~10.0g/10min,等规度为95.0~98.0%。
添加剂由抗氧剂、辅抗氧剂A和B以及吸酸剂组成,其中:
主抗氧为1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯,
辅抗氧剂A为四(2,4-二叔丁基酚)-4,4'-联苯基二亚磷酸酯,
辅抗氧剂B为N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺,
吸酸剂为硬脂酸钙。
各实施例添加剂的组分配比及添加剂的加入量见表1,其中添加剂的组分配比为当主抗氧剂为100重量份时其它组分的重量份;添加剂的加入量为当聚丙烯树脂基料为100重量份时添加剂的重量份。表1中“α-烯烃(Cn)”表示碳链长度为n的α-直链烯烃。
各实施例得到的聚丙烯树脂成品,采用高温蒸煮CPP薄膜生产工艺(工艺参数:生产线速度:100m/min;生产线温度设定:挤出机:240~250℃;模头:240℃;铸片机:30℃。)加工薄膜,薄膜厚度为70μm。在时效后测试薄膜的主要性能指标,结果见表2。
表1.
表2.
对于本领域技术人员显而易见的是,在不背离本发明的范围和精神的前提下,可对其进行各种修改和变动,上述各项技术特征之间的组合及根据上述内容所完成的其它技术方案改变均属本发明范围。
Claims (5)
1.一种用于制造高温蒸煮CPP薄膜的聚丙烯树脂组合物,包括聚丙烯树脂基料和添加剂,聚丙烯树脂基料与添加剂的重量比为100∶0.08~0.20,
所述的聚丙烯树脂基料,其熔体流动速率为7.0~10.0g/10min,等规度为95.0~98.0%;
所述的添加剂包括主抗氧剂、辅抗氧剂A、辅抗氧剂B、吸酸剂,其中:
主抗氧为1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯,辅抗氧剂A为四(2,4-二叔丁基酚)-4,4'-联苯基二亚磷酸酯,辅抗氧剂B为N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺,吸酸剂为硬脂酸钙;
添加剂的组分配比以重量份计,当主抗氧剂为100份时,辅抗氧剂A为40~55份,辅抗氧剂B为20~35份,吸酸剂为50份。
2.根据权利要求1所述的聚丙烯树脂组合物,其特征在于,聚丙烯树脂基料为由93~99.5wt%的丙烯与0.5~7wt%的C4-C8α-直链烯烃共聚而成的聚丙烯共聚物。
3.根据权利要求1或2所述的聚丙烯树脂组合物,其特征在于,所述的添加剂的组分配比以重量份计,当主抗氧剂为100份时,辅抗氧剂A为45~50份,辅抗氧剂B为25~35份。
4.根据权利要求1至3任一项所述的聚丙烯树脂组合物,其特征在于,所述的聚丙烯树脂基料与添加剂的重量比为100∶0.10~0.15。
5.一种高温蒸煮CPP薄膜,其特征在于,薄膜的原料为权利要求1-4任一项所述的聚丙烯树脂组合物。
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