CN104861279B - 一种双色抗菌eva鞋及其制备方法 - Google Patents
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Abstract
本发明涉及有机高分子化合物技术领域，提供一种双色抗菌EVA鞋及其制备方法，由原料EVA、乙烯‑丁烯共聚物、1,2‑聚丁二烯、抗菌剂、氯化聚乙烯、发泡剂、交联剂、硬脂酸锌、硬脂酸、耐磨剂、滑石粉、颜料经过密炼、开炼、造粒制得两种不同颜色的抗菌EVA料米，再分别倒入双色EVA注射机台的不同吸料桶，经一次射出得到双色抗菌EVA鞋，所述双色抗菌EVA鞋对大肠杆菌和金黄色葡萄球菌的抗菌率都超过99%，具有良好的耐水耐候持效抗菌性能，而且具有质轻、综合性能好、生产效率高、产品合格率高等特点，特别适合生产与人体皮肤直接接触的EVA鞋，如凉鞋、拖鞋、室内鞋等，轻便舒适、性价比高。
Description
技术领域
本发明属于有机高分子化合物技术领域，特别涉及一种双色抗菌EVA鞋及其制备方法。
背景技术
鞋，是每个人都要穿着的生活用品，人的一生有2／3的时间穿着鞋子。大多数人在穿用鞋靴的过程中，尤其是在夏天和运动后，由于汗液分泌量剧增，微生物高速繁殖，大量分解汗液中的有机物而产生恶臭，长此以往甚至导致脚臭、脚癣、香港脚、脚气等一系列疾患，直接影响着人们的身心健康。究其原因，EVA是结晶性聚合物，具有高结晶度，使得能穿过气体的小孔比较少，即透气性能差，温度、湿度正适合容易细菌繁殖。人们想到经常换鞋垫来改善，但治标不治本。如果是与人体皮肤直接接触的EVA凉鞋、拖鞋、室内鞋，这类鞋具有轻便舒适、性价比高等优势，广受大家喜爱，但是细菌短时间高速繁殖导致发臭的问题就束手无策了。
由于EVA发泡材料生产过程中射出或模压发泡温度较高(165～180℃)，有机小分子抗菌剂和天然抗菌剂的耐热性差，难以满足加工工艺要求；银系无机抗菌剂具有耐热性好、抗菌持续性强、安全性高等特点，但存在无机抗菌粉体的比表面积大、溶出的重金属离子银铜危害人们健康、银系抗菌剂易变色、使用工艺复杂等缺点，所以，目前市场上的 EVA发泡材料大部分不具有抗菌功能。因此如何克服现有技术的不足是目前高分子材料技术领域亟需解决的问题。
发明内容
本发明的目的就是针对现有技术存在的不足而提供一种双色抗菌EVA鞋及其制备方法，所述双色抗菌EVA鞋对大肠杆菌和金黄色葡萄球菌的抗菌率都超过99%，具有良好的耐水耐候持效抗菌性能，而且具有质轻、综合性能好、生产效率高、产品合格率高等特点，特别适合生产与人体皮肤直接接触的鞋，如EVA凉鞋、拖鞋、室内鞋等，轻便舒适、性价比高。
为实现上述目的，本发明采取的解决方案为：一种双色抗菌EVA鞋，由以下原料组成制得：原料EVA、乙烯-丁烯共聚物、1,2-聚丁二烯、抗菌剂、氯化聚乙烯、发泡剂、交联剂、硬脂酸锌、硬脂酸、耐磨剂、滑石粉、颜料。
进一步的是，各原料的重量份如下：
原料EVA 50 份
乙烯-丁烯共聚物 15 - 25 份
1,2-聚丁二烯 15 - 20 份
抗菌剂 3 - 8 份
氯化聚乙烯 3 - 5 份
发泡剂 2 - 3 份
交联剂 0.5 - 1.5 份
硬脂酸锌 1–1.5 份
硬脂酸 1–1.5 份
耐磨剂 1 - 3 份
滑石粉 10 - 15份
颜料 0.2 - 2份。
进一步优选的，各组分按下列重量份配置:
原料EVA 50 份
乙烯-丁烯共聚物 20 份
1,2-聚丁二烯 17 份
抗菌剂 4 份
氯化聚乙烯 4 份
发泡剂 2.4 份
交联剂 0.8 份
硬脂酸锌 1.2 份
硬脂酸 1.2 份
耐磨剂 3 份
滑石粉 13份
颜料 0.4份。
进一步的是：乙烯-丁烯共聚物是熔点高于70度的乙烯-丁烯共聚物。
进一步的是：所述1,2-聚丁二烯是1,2-单元超过90%的聚丁二烯橡胶。
进一步的是：所述抗菌剂为高分子抗菌剂。
进一步的是：所述抗菌剂至少包括季铵盐类高分子抗菌剂、季磷盐类高分子抗菌剂、吡啶类高分子抗菌剂中的一种。
进一步的是：所述氯化聚乙烯是淄博济维泽化工有限公司的氯化聚乙烯135B。
进一步的是：所述发泡剂是AC发泡剂。
进一步的是：所述交联剂是BIBP。
进一步的是：所述耐磨剂是耐磨剂AG209。
进一步的是：所述颜料至少包括无机颜料、有机小分子颜料中的一种。
进一步的是：所述有机小分子颜料的热稳定性高于180℃。
一种制备所述双色抗菌EVA鞋的制备方法，包括步骤：
步骤1：制备两种不同颜色的抗菌EVA料米，先将原料EVA、乙烯-丁烯共聚物、1,2-聚丁二烯、抗菌剂、氯化聚乙烯、硬脂酸锌、硬脂酸、耐磨剂、滑石粉、颜料混合进行密炼，调整密炼温度控制为 95-98℃，保持 4-6min，然后加入交联剂以及发泡剂，继续密炼升温，出料温度为100-104℃，密炼结束后进行开炼、造粒，得到抗菌EVA料米A；同上述方法，更换颜料种类，得到抗菌EVA料米B；
步骤2：两种不同颜色的抗菌EVA料米A和B分别倒入双色EVA注射机台的不同吸料桶，经一次射出得到双色抗菌EVA鞋。
通过采取前述技术方案，本发明具有如下有益效果：
1，本发明双色抗菌EVA鞋使用抗菌效率高的高分子抗菌剂、氯化聚乙烯作为辅助抗菌剂，抗菌效果显著，安全无毒长效，对大肠杆菌和金黄色葡萄球菌的抗菌率都超过99%，具有良好的耐水耐候持效抗菌性能。当双色抗菌EVA鞋在自来水中浸泡或者太阳暴晒后，内部深层抗菌分子可以缓慢地向EVA发泡材料表面迁移，使抗菌能力得到补充，从而使EVA发泡材料保持良好的抗菌性能，特别适合生产与人体皮肤、袜子直接接触的鞋，如EVA凉鞋、拖鞋、室内鞋等。
2，按照本发明所述制备方法，经一次射出得到双色抗菌EVA鞋，产品合格率超过95%，明显高于同行的双色EVA鞋产品合格率，且颜色稳定性好，提升了鞋底的视觉美观性，同时大大提高了生产效率，适合批量化生产。
具体实施方式
现结合具体实施例对本发明进一步说明。
实施例1：
本实施例中， 双色抗菌EVA鞋由以下组分按重量份组成：
EVA 5110 15 份
EVA 7470 35 份
乙烯-丁烯共聚物ENR7256 20 份
1,2-聚丁二烯 RB820 17 份
三丁基乙烯基苄基氯-甲基丙烯酸甲酯共聚物的三丁基膦盐抗菌剂 4 份
氯化聚乙烯 135B 4 份
发泡剂Ac 2.4 份
交联剂BIBP 0.8 份
硬脂酸锌 1.2 份
硬脂酸 1.2 份
耐磨剂AG209 3 份
滑石粉 13份
颜料酞菁蓝 0.4份。
双色抗菌EVA鞋的制备方法，包括步骤：
步骤1：制备两种不同颜色的抗菌EVA料米，先将上述配方中除了交联剂以及发泡剂之外的其他原料混合进行密炼，调整密炼温度控制为96℃，保持6min，然后加入交联剂以及发泡剂，继续密炼升温，出料温度为102℃，密炼结束后进行开炼、造粒，得到抗菌EVA料米A。
同上述方法，更换颜料为永固黄，得到抗菌EVA料米B。
步骤2：两种不同颜色的抗菌EVA料米A和B分别倒入双色EVA注射机台的不同吸料桶，经一次射出得到双色抗菌EVA鞋。
上述制备得到的双色抗菌EVA鞋，密度0.22g/cm3，硬度 57，DIN耐磨236 mm3，尺寸收缩1.1%，回弹率53%， 撕裂强度6.5N/mm，动态止滑系数平滑干式0.68湿式0.53，静态止滑系数干式0.56湿式0.46，对大肠杆菌的抗菌率99.5%，对金黄色葡萄球菌的抗菌率99.3%。
实施例2：
本实施例中，一种双色抗菌EVA鞋的制备方法与实施例1中的制备方法相同，所不同的是：
抗菌EVA料米A的部分成分更改为：EVA 7470 50份、乙烯-丁烯共聚ENR7256
20份、1,2-聚丁二烯 RB830 15份、三丁基乙烯基苄基氯-甲基丙烯酸甲酯共聚物的三丁基膦盐抗菌剂 6份、炭黑(颜料) 0.8份；
抗菌EVA料米B的颜料为荧光青0.2份。
上述制备得到的双色抗菌EVA鞋，密度0.23g/cm3，硬度 55，DIN耐磨266 mm3，尺寸收缩1.5%，回弹率55%，撕裂强度5.8N/mm，动态止滑系数平滑干式0.63湿式0.49，静态止滑系数干式0.50湿式0.42，对大肠杆菌的抗菌率98.5%，对金黄色葡萄球菌的抗菌率98.0%。
实施例3：
本实施例中，一种双色抗菌EVA鞋的制备方法与实施例1中的制备方法相同，所不同的是：
抗菌EVA料米A的部分成分更改为：EVA E210F 15份、 EVA PA470 35份、乙烯-丁烯共聚物ENR7086 20份、季铵盐类高分子抗菌剂ASQA 6份、氯化聚乙烯3份、滑石粉10份，得到抗菌EVA料米A；
上述制备得到的双色抗菌EVA鞋，密度0.21g/cm3，硬度 54，DIN耐磨282 mm3，尺寸收缩1.5%，回弹率56%， 撕裂强度5.3N/mm，动态止滑系数平滑干式0.55湿式0.43，静态止滑系数干式0.47湿式0.38，对大肠杆菌的抗菌率99.9%，对金黄色葡萄球菌的抗菌率99.8%。
实施例4：
本实施例中，一种双色抗菌EVA鞋的制备方法与实施例1中的制备方法相同，所不同的是：
抗菌EVA料米A的部分成分更改为：乙烯-丁烯共聚物ENR7256 15份、1,2-聚丁二烯RB820 20份、三丁基乙烯基苄基氯-甲基丙烯酸甲酯共聚物的三丁基膦盐抗菌剂 3份、氯化聚乙烯 5份、耐磨剂AG209 1份、滑石粉15份；
抗菌EVA料米B的颜料为钛白粉2份。
上述制备得到的双色抗菌EVA鞋，密度0.22g/cm3，硬度 59，DIN耐磨324 mm3，尺寸收缩1.3%，回弹率52%， 撕裂强度7.6N/mm，动态止滑系数平滑干式0.72湿式0.65，静态止滑系数干式0.68湿式0.55，对大肠杆菌的抗菌率95.1%，对金黄色葡萄球菌的抗菌率95.9%。
将上述实施例1 ～ 4 的数据整理后，得到如下表1（注：硬度采用GS-701N硬度计测试，DIN耐磨按照GB/T 9867：2001测试，尺寸收缩按照ISO 20873：2001测试，回弹率测试采用GT-7042-RE型冲击弹性试验机，撕裂强度按照GB/T 10808-2006测试，动态止滑系数按照TM144：2011测试，静态止滑系数按照ASTM F1677：2005测试，参照国家卫生部2002年11月颁布的《消毒技术规范》中的振荡烧瓶法1测定抗菌EVA发泡鞋的抗菌率）：
表1 ：实施例1～4制备的双色抗菌EVA鞋的性能参数对照表
综上所述，按照本发明的双色抗菌EVA鞋的制备方法，能够制得对大肠杆菌和金黄色葡萄球菌的抗菌率都超过99%的双色抗菌EVA鞋，具有良好的耐水耐候持效抗菌性能，而且具有质轻、综合性能好、生产效率高、产品合格率高等特点，特别适合生产与人体皮肤直接接触的鞋，如EVA凉鞋、拖鞋、室内鞋等，轻便舒适、性价比高。
本发明实施例中列举的抗菌剂种类分量选择只是其中几种方案，所述抗菌剂使用其他类型的季磷盐类高分子抗菌剂，或者季铵盐类高分子抗菌剂、吡啶类高分子抗菌剂，或者两种抗菌剂共混，都具有很好的抗菌性能。
以上所记载，仅为利用本创作技术内容的实施例，任何熟悉本项技艺者运用本创作所做的修饰、变化，皆属本创作主张的专利范围，而不限于实施例所揭示者。
Claims (5)
1.一种双色抗菌EVA鞋，其特征在于，由以下原料组成制得：
原料EVA 50 份
乙烯-丁烯共聚物 15 - 25 份
1,2-聚丁二烯 15 - 20 份
抗菌剂 3 - 8 份
氯化聚乙烯 3 - 5 份
发泡剂 2 - 3 份
交联剂 0.5 - 1.5 份
硬脂酸锌 1–1.5 份
硬脂酸 1–1.5 份
耐磨剂 1 - 3 份
滑石粉 10 - 15份
颜料 0.2 - 2份。
2.根据权利要求1所述的双色抗菌EVA鞋，其特征在于：由以下组分按下列重量份原料制备而成:
原料EVA 50 份
乙烯-丁烯共聚物 20 份
1,2-聚丁二烯 17 份
抗菌剂 4 份
氯化聚乙烯 4 份
发泡剂 2.4 份
交联剂 0.8 份
硬脂酸锌 1.2 份
硬脂酸 1.2 份
耐磨剂 3 份
滑石粉 13份
颜料 0.4份。
3.根据权利要求1或2所述双色抗菌EVA鞋，其特征在于：所述1,2-聚丁二烯是1,2-单元超过90%的聚丁二烯橡胶；所述颜料至少包括无机颜料、热稳定性高于180℃的有机小分子颜料中的一种。
4.根据权利要求1或2所述双色抗菌EVA鞋，其特征在于：所述抗菌剂为高分子抗菌剂。
5.一种制备权利要求1-4任一所述双色抗菌EVA鞋的制备方法，其特征在于，包括步骤：
步骤1：制备两种不同颜色的抗菌EVA料米，先将原料EVA、乙烯-丁烯共聚物、1,2-聚丁二烯、抗菌剂、氯化聚乙烯、硬脂酸锌、硬脂酸、耐磨剂、滑石粉、颜料混合进行密炼，调整密炼温度控制为 95-98℃，保持 4-6min，然后加入交联剂以及发泡剂，继续密炼升温，出料温度为100-104℃，密炼结束后进行开炼、造粒，得到抗菌EVA料米A；同上述方法，更换颜料种类，得到抗菌EVA料米B；
步骤2：两种不同颜色的抗菌EVA料米A和B分别倒入双色EVA注射机台的不同吸料桶，经一次射出得到双色抗菌EVA鞋。
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