CN111572138B - 一种珠光聚酰胺薄膜及其制备方法 - Google Patents
一种珠光聚酰胺薄膜及其制备方法 Download PDFInfo
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Abstract
本发明提供一种珠光聚酰胺薄膜及其制备方法,其中,珠光聚酰胺薄膜从上至下依次为上表层、芯层和下表层;以质量份数计,所述芯层由70~90份聚酰胺树脂和15~35份的珠光母料组成;所述珠光母料由55~85份聚酰胺树脂、20~30份硫酸钡、5~15份含聚4‑甲基‑1‑戊烯结构单元的共聚物和0.1~1份超分散剂组成;所述上表层和下表层均为抗粘连层,由100份聚酰胺树脂和3~5份防粘母料组成。本发明制备得到的珠光聚酰胺薄膜具有柔和悦目的珍珠光泽和较好的遮光性,同时具有拉伸强度大以及对氧气具有较好的阻隔性能的优点,可广泛应用于食品、礼品包装等产品。
Description
技术领域
本发明涉及软包装材料领域,特别涉及一种珠光聚酰胺薄膜及其制备方法。
背景技术
珠光膜由于具有独特的珠光效果,且对产品的包装具有较好的装饰效果,广泛应用于各类包装。例如BOPP珠光膜被广泛应用于冰激凌、热封标签、甜食、饼干、风味小吃包装等包装。目前,随着市场的不断开发,珠光薄膜的种类也越来越多,应用领域不断拓宽,市场前景广阔。
然而,现有报道的珠光膜主要是涉及双向拉伸聚丙烯(BOPP)珠光膜,例如专利CN110435274 A,公开日为2019年11月12日,公开了一种珠光热封膜。鲜有关于具有珠光效果的双向拉伸聚酰胺薄膜(BOPA)的报道。与BOPP薄膜相比,BOPA薄膜具有更大的拉伸强度,更加优异的氧气阻隔性能和耐穿刺性能,更高的耐热性等优点。因此,将珠光性能和BOPA薄膜本身的性能优点相结合,赋予BOPA薄膜珠光的效果,有望获得一种性能更加优异的珠光膜,扩宽BOPA薄膜的功能和应用领域。
发明内容
为解决背景技术中提到的问题,本发明提供一种珠光聚酰胺薄膜,其膜层结构从上至下依次为上表层、芯层和下表层;
其中,按质量份数计:
所述芯层由70~90份聚酰胺树脂和15~35份的珠光母料组成;
所述珠光母料由55~85份聚酰胺树脂、20~30份硫酸钡、5~15份含聚4-甲基-1-戊烯结构单元的共聚物和0.1~1份超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份聚酰胺树脂和3~5份防粘母料组成。
进一步地,所述硫酸钡为湿法改性的活化硫酸钡,平均粒径为0.5~3μm。
进一步地,所述含聚4-甲基-1-戊烯结构单元的共聚物为聚4-甲基-1-戊烯、4-甲基-1-戊烯类无规共聚物、4-甲基-1-戊烯与α-烯烃共聚物中的至少一种。
进一步地,所述聚酰胺树脂为尼龙6、尼龙612、尼龙66、尼龙610、尼龙12、尼龙1212、尼龙6/66、尼龙66/6、尼龙MXD-6和尼龙1010中的至少一种。
进一步地,所述超分散剂的分子结构分为两部分:其中一部分为锚固基团,有胺基、磺基或多元醇基团;另一部分为溶剂化链,有聚酯、聚醚、聚烯烃或聚丙烯酸酯。
进一步地,所述上表层厚度为1.5~3μm;所述芯层厚度为6~25μm;所述下表层厚度为1.5~3μm。
本发明还提供一种上述的珠光聚酰胺薄膜的制备方法,包括以下步骤:
步骤1、将上表层、芯层和下表层各层原料按比例分别进行混合,分别通过各自的挤出机熔融挤出,经过T型模头流出,并经过表面温度为15~40℃的激冷辊冷却,形成未拉伸薄膜铸片;
步骤2、将未拉伸薄膜铸片在160~200℃加热下进行分步或同步拉伸,拉伸倍率为2.5×2.5-3.5×3.5;
步骤3、将拉伸后的薄膜进行热定型,其中定型温度为170~210℃,定型时间为3-20s,松弛率为1%-3%,得到珠光聚酰胺薄膜。
进一步地,所述芯层采用的珠光母料制备方法包括以下步骤:
S10、将聚酰胺树脂与超分散剂依次投入低速混合机中混1min,再依次将硫酸钡和含聚4-甲基-1-戊烯结构单元的共聚物投入低速混合机中混5min,其中低速混合机的转速为100转/分钟;
S20、将混合好的混合物投入到同向双螺杆挤出机的加料斗中,经熔融挤出、造粒后,在100℃除湿机中干燥3小时,备用;其中,同向双螺杆挤出机的加工温度为210~255℃,螺杆转速为350~550转/分钟。
进一步地,将得到的珠光聚酰胺薄膜的至少一个表面进行电晕处理。
进一步地,制得的珠光聚酰胺薄膜厚度为12-30μm。
与现有技术相比,本发明具有如下有益效果:
1、本发明采用特殊的珠光母料,珠光母料中的含聚4-甲基-1-戊烯结构单元的共聚物和硫酸钡与聚酰胺树脂的粘合力较低,拉伸过程中,易形成空穴,光线照射时,发生干涉现象,产生珠光效果。同时,本发明使用聚4-甲基-1-戊烯结构单元的共聚物和硫酸钡,避免在制备珠光母粒中大量使用珠光填料,在生产BOPA珠光薄膜时,加入本发明所制的珠光母粒可以有效避免滤网的堵塞和珠光膜的破裂。
2、相比BOPP珠光膜,本发明制备的珠光聚酰胺薄膜具有更加优异的氧气阻隔性能和更高的拉伸强度和耐热性。
3、本发明制备的珠光聚酰胺薄膜具有柔和悦目的珍珠光泽和较好的遮光性,还对氧气具有较好的阻隔性能,可广泛应用于食品、礼品包装等产品。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明实施例的珠光聚酰胺薄膜的制备方法,包括以下步骤:
(一)珠光母料的制备:
S10、将聚酰胺树脂与聚氨酯超分散剂依次投入低速混合机中混1min,再依次将硫酸钡和含聚4-甲基-1-戊烯结构单元的共聚物投入低速混合机中混5min,其中低速混合机的转速为100转/分钟;
S20、将混合好的混合物投入到同向双螺杆挤出机的加料斗中,经熔融挤出、造粒后,在100℃除湿机中干燥3小时,备用;其中,同向双螺杆挤出机的加工工艺为:加工温度:210~255℃,螺杆转速为350~550转/分钟。
(二)珠光聚酰胺薄膜的制备:
步骤1、将上表层、芯层和下表层各层原料按比例分别进行混合,分别通过各自的挤出机熔融挤出,经过T型模头流出,并经过表面温度为15~40℃的激冷辊冷却,形成未拉伸薄膜铸片;
步骤3、将未拉伸薄膜铸片在160~200℃加热下进行分步或同步拉伸,拉伸倍率为2.5×2.5-3.5×3.5;
步骤4、将拉伸后的薄膜进行热定型,其中定型温度为170~210℃,定型时间为3-20s,松弛率为1%-3%,并对薄膜的至少一个表面进行电晕处理,得到所述的珠光聚酰胺薄膜,薄膜厚度为12-30μm。
本发明提供以下珠光聚酰胺薄膜的实施例:
实施例1
一种珠光聚酰胺薄膜,从上到下依次由上表层、芯层和下表层构成;其中,按质量份数计,芯层由70份尼龙6和15份的珠光母料组成;
所述珠光母料由75份尼龙6,30份硫酸钡,5份聚4-甲基-1-戊烯,0.5份聚氨酯超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份尼龙6/66和3份防粘母料组成。
按照上述制备方法制备样品,得到薄膜的总厚度为15μm,其中表层1和表层2的厚度均为1.5μm,芯层的厚度为12μm。
实施例2
一种珠光聚酰胺薄膜,从上到下依次由上表层、芯层和下表层构成;其中,按质量份数计,芯层由90份尼龙6/66和35份的珠光母料组成;
所述珠光母料由85份尼龙6,20份硫酸钡,15份聚4-甲基-1-戊烯,1份聚氨酯超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份尼龙6和5份防粘母料组成。
按照上述制备方法制备样品,得到薄膜的总厚度为15μm,其中表层1和表层2的厚度均为3μm,芯层的厚度为9μm。
比较例1
市售BOPP珠光膜
对比例2
一种珠光聚酰胺薄膜,从上到下依次由上表层、芯层和下表层构成;其中,按质量份数计,芯层由90份聚尼龙6和15份的助剂组成;
所述助剂由80份尼龙6,20份硫酸钡,1份聚氨酯超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份尼龙6和3份防粘母料组成。
其中助剂的制备方法参照实施例中珠光母料的制备方法,薄膜的制备方法参照实施例中薄膜的制备方法,得到薄膜的总厚度为15μm,其中表层1和表层2的厚度均为1.5μm,芯层的厚度为12μm。
对比例3
一种珠光聚酰胺薄膜,从上到下依次由上表层、芯层和下表层构成;其中,按质量份数计,芯层由90份聚尼龙6和15份的助剂组成;
所述助剂由80份尼龙6,10份聚4-甲基-1-戊烯,1份聚氨酯超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份尼龙6和3份防粘母料组成。
其中助剂的制备方法参照实施例中珠光母料的制备方法,薄膜的制备方法参照实施例中薄膜的制备方法,得到薄膜的总厚度为15μm,其中表层1和表层2的厚度均为1.5μm,芯层的厚度为12μm。
将上述实施例和对比例进行相关项目测试,测试方法为:
拉伸性能:按照GBT 1040.3-2006标准测试;
透光率和雾度:按照GBT 2410-2008标准测试;
光泽度:按照ASTM D2457-2003标准测试;
氧气透过率:按照ASTM F1927标准测试;
珠光效果评价:薄膜呈现白色、柔和悦目的珍珠般光泽,则珠光效果好(记为Δ),反之,则珠光效果差(记为×)
其测试结果如表1所示:
表1
备注:*代表氧气透过率太大,超过透氧仪量程无法测量
根据表1可知,对比例2和对比例3的助剂与本发明的珠光母料相比,分别缺少了4-甲基-1-戊烯和硫酸钡,其制备的薄膜不具有珠光效果;本发明通过聚酰胺树脂、硫酸钡、含聚4-甲基-1-戊烯结构单元的共聚物和聚氨酯超分散剂的特殊组合获得了一种珠光母料,能够制备一种珠光聚酰胺薄膜。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种珠光聚酰胺薄膜,其特征在于,其膜层结构从上至下依次为上表层、芯层和下表层;
其中,按质量份数计:
所述芯层由70~90份聚酰胺树脂和15~35份的珠光母料组成;
所述珠光母料由55~85份聚酰胺树脂、20~30份硫酸钡、5~15份含聚4-甲基-1-戊烯结构单元的聚合物和0.1~1份超分散剂组成;
所述上表层和下表层均为抗粘连层,由100份聚酰胺树脂和3~5份防粘母料组成。
2.根据权利要求1所述的珠光聚酰胺薄膜,其特征在于,所述硫酸钡为湿法改性的活化硫酸钡,平均粒径为0.5~3μm。
3.根据权利要求1所述的珠光聚酰胺薄膜,其特征在于,所述含聚4-甲基-1-戊烯结构单元的聚合物为聚4-甲基-1-戊烯、4-甲基-1-戊烯与α-烯烃共聚物中的至少一种。
4.根据权利要求1所述的珠光聚酰胺薄膜,其特征在于,所述聚酰胺树脂为尼龙6、尼龙612、尼龙66、尼龙610、尼龙12、尼龙1212、尼龙6/66、尼龙66/6、尼龙MXD-6和尼龙1010中的至少一种。
5.根据权利要求1所述的珠光聚酰胺薄膜,其特征在于,所述超分散剂的分子结构分为两部分:其中一部分为锚固基团,有胺基、磺基或多元醇基团;另一部分为溶剂化链,有聚酯、聚醚、聚烯烃或聚丙烯酸酯。
6.根据权利要求1所述的珠光聚酰胺薄膜,其特征在于,所述上表层厚度为1.5~3μm;所述芯层厚度为6~25μm;所述下表层厚度为1.5~3μm。
7.一种如权利要求1-6任一项所述的珠光聚酰胺薄膜的制备方法,其特征在于,包括以下步骤:
步骤1、将上表层、芯层和下表层各层原料按比例分别进行混合,分别通过各自的挤出机熔融挤出,经过T型模头流出,并经过表面温度为15~40℃的激冷辊冷却,形成未拉伸薄膜铸片;
步骤2、将未拉伸薄膜铸片在160~200℃加热下进行分步或同步拉伸,拉伸倍率为2.5×2.5-3.5×3.5;
步骤3、将拉伸后的薄膜进行热定型,其中定型温度为170~210℃,定型时间为3-20s,松弛率为1%-3%,得到珠光聚酰胺薄膜。
8.根据权利要求7的珠光聚酰胺薄膜的制备方法,其特征在于,所述芯层采用的珠光母料制备方法包括以下步骤:
S10、将聚酰胺树脂与超分散剂依次投入低速混合机中混1min,再依次将硫酸钡和含聚4-甲基-1-戊烯结构单元的聚合物投入低速混合机中混5min,其中低速混合机的转速为100转/分钟;
S20、将混合好的混合物投入到同向双螺杆挤出机的加料斗中,经熔融挤出、造粒后,在100℃除湿机中干燥3小时,备用;其中,同向双螺杆挤出机的加工温度为210~255℃,螺杆转速为350~550转/分钟。
9.根据权利要求7的珠光聚酰胺薄膜的制备方法,其特征在于,将得到的珠光聚酰胺薄膜的至少一个表面进行电晕处理。
10.根据权利要求7的珠光聚酰胺薄膜的制备方法,其特征在于,制得的珠光聚酰胺薄膜厚度为12-30μm。
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