CN104829884B - 一种抗菌防霉橡胶鞋底及其制备方法 - Google Patents
一种抗菌防霉橡胶鞋底及其制备方法 Download PDFInfo
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Abstract
本发明涉及有机高分子化合物技术领域，提供一种抗菌防霉橡胶鞋底及其制备方法，由原料异戊橡胶、丁苯橡胶、丙烯腈‑丁二烯‑苯乙烯三元共聚物、溴化丁基橡胶、氯化聚乙烯橡胶、抗菌剂、白炭黑、矿物油、防老剂、防霉剂、聚乙二醇、硅烷偶联剂、聚乙烯蜡、氧化锌、硫磺、硫化促进剂组成，所述抗菌防霉橡胶鞋底对大肠杆菌和金黄色葡萄球菌的抗菌率超过99%、对白色念珠菌的抗菌率超过85%，具有良好的耐水耐候持效抗菌性能，防霉效果显著，而且具有较好的止滑耐磨性能，特别适合生产户外鞋、作训鞋。
Description
技术领域
本发明属于橡胶鞋底领域，特别涉及一种抗菌防霉橡胶鞋底及其制备方法。
背景技术
橡胶等高分子材料加工的制品，在温度高、湿度大、背阴等条件下极易受到霉菌、细菌的攻击，助长它们的繁殖，使制品的表面变色、产生斑点甚至出现细孔，从而影响了橡胶制品的正常使用。其霉变的起因是由于霉菌抱子附着于制品的表面，而后不断繁殖造成的。天然橡胶含有少量的蛋白质、脂肪酸、糖分等有利于霉菌繁殖的物质，对微生物的敏感性较大，易受到霉菌的侵蚀。合成橡胶通常是不易受霉菌侵害的，但由于制品中往往加入了增塑剂、稳定剂、填充剂、润滑剂等加工助剂，尤其是增塑剂，这类物质对霉菌较敏感，致使合成橡胶制品也易受到霉菌的侵蚀而破坏。橡胶鞋底也不例外，储存运输过程的高温高湿环境容易滋生细菌，一旦橡胶鞋底发霉，将很难清洗干净，严重影响成品鞋的美观，通常只能当废品处理，造成较大的材料和金钱浪费。
专利CN 102558619 B公开了一种抗菌防霉抗藻橡胶材料，添加多菌灵、N-辛基异噻唑啉酮和敌草隆等有机小分子抗菌剂，热稳定性差，使用工艺复杂，而且易产生耐药性、分解产物有毒。专利CN 102002192 B公开了一种具有抗菌防霉性能的工程橡胶材料，使用纳米复合耐高温抗菌材料，这种以无机材料、稀土、金属盐等为主要原料的抗菌材料，材料的颜色稳定性差，且防霉效果一般，仅达到防霉2级。专利CN 102977436 A公开的防霉橡胶使用有毒的铅化合物，铅被人体吸收后会在肝脏内积累，引起慢性铅中毒。专利CN104177835 A公开的防霉橡胶使用大量防霉剂(20-50份),削弱了影响橡胶材料本身的良好力学性能。
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抗菌防霉橡胶鞋底及其制备方法，所述抗菌防霉橡胶鞋底对大肠杆菌和金黄色葡萄球菌的抗菌率都超过99％，对白色念珠菌的抗菌率超过85％，具有良好的耐水耐候持效抗菌性能，防霉效果显著，而且具有较好的止滑耐磨性能，特别适合生产户外鞋、作训鞋。
为实现上述目的，本发明采取的解决方案为：一种抗菌防霉橡胶鞋底，由以下原料组成制得：异戊橡胶、丁苯橡胶、丙烯腈-丁二烯-苯乙烯三元共聚物、溴化丁基橡胶、氯化聚乙烯橡胶、抗菌剂、白炭黑、矿物油、氧化锌、防老剂、防霉剂、聚乙二醇、硅烷偶联剂、聚乙烯蜡、硫磺、硫化促进剂。
进一步的是，各原料的重量份如下：
进一步优选的，各组分按下列重量份配置:
进一步的是：所述丙烯腈-丁二烯-苯乙烯三元共聚物的丙烯腈含量大于18％。
进一步的是：所述丙烯腈-丁二烯-苯乙烯三元共聚物的苯乙烯含量大于20％。
进一步的是：所述溴化丁基橡胶至少包括朗盛溴化丁基X2、溴化丁基2030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140A。
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：所述防霉剂是防霉剂A26。
一种制备前述抗菌防霉橡胶鞋底的制备方法，按照配方比例称量异戊橡胶、丁苯橡胶、丙烯腈-丁二烯-苯乙烯三元共聚物、溴化丁基橡胶、氯化聚乙烯橡胶、抗菌剂、白炭黑、矿物油、氧化锌、防老剂、防霉剂、聚乙二醇、硅烷偶联剂、聚乙烯蜡、硫磺、硫化促进剂，将组分材料除硫磺、硫化促进剂以外的胶料放入密炼机中密炼，108-110度排胶，室温放置24小时，然后在双辊开炼机上混炼，并加入准确称量的硫磺、硫化促进剂，混炼均匀后，以均匀片状出片，最后将物料裁成鞋底形状放入橡胶鞋模中硫化成型，即得到抗菌防霉橡胶鞋底。
通过采取前述技术方案，本发明具有的有益效果：本发明抗菌防霉橡胶鞋底使用抗菌效率高的高分子抗菌剂，氯化聚乙烯和溴化丁基橡胶作为辅助抗菌剂，抗菌效果显著，耐热性好、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％，对白色念珠菌的抗菌率超过85％，具有良好的耐水耐候持效抗菌性能，防霉效果显著，当抗菌防霉橡胶鞋底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鞋底表面迁移，使抗菌能力得到补充，从而使橡胶鞋底保持良好的抗菌性能，杜绝鞋底长霉。
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，抗菌防霉橡胶鞋底由以下组分按重量份组成：
抗菌防霉橡胶鞋底的制备方法，按照配方比例称量异戊橡胶、丁苯橡胶、丙烯腈-丁二烯-苯乙烯三元共聚物、溴化丁基橡胶、氯化聚乙烯橡胶、抗菌剂、白炭黑、矿物油、氧化锌、防老剂、防霉剂、聚乙二醇、硅烷偶联剂、聚乙烯蜡、硫磺、硫化促进剂，将组分材料除硫磺、硫化促进剂以外的胶料放入密炼机中密炼，108度排胶，室温放置24小时，然后在双辊开炼机上混炼，并加入准确称量的硫磺、硫化促进剂，混炼均匀后，以均匀片状出片，最后将物料裁成鞋底形状放入橡胶鞋模中硫化成型，即得到抗菌防霉橡胶鞋底。
上述制备得到的抗菌防霉橡胶鞋底，密度1.11g/cm3，硬度64，DIN耐磨198mm3，撕裂强度72N/mm，氙灯老化试验无吐霜现象，臭氧老化试验无龟裂现象，耐折6万次无裂纹，动态止滑系数平滑干式0.82湿式0.54，对大肠杆菌的抗菌率99.5％，对金黄色葡萄球菌的抗菌率99.0％，对大肠杆菌的抗菌率88.6％，防霉级别0级。
实施例2：
本实施例中，一种抗菌防霉橡胶鞋底的制备方法与实施例1中的制备方法相同，所不同的是配方原料中：
丙烯腈-丁二烯-苯乙烯三元共聚物2250 20份、溴化丁基橡胶X2 12份、乙烯基苄基氯-甲基丙烯酸甲酯共聚物的三苯基膦盐抗菌剂7份、白炭黑20份。
上述制备得到的抗菌防霉橡胶鞋底，密度1.12g/cm3，硬度66，DIN耐磨201mm3，撕裂强度75N/mm，氙灯老化试验无吐霜现象，臭氧老化试验无龟裂现象，耐折6万次无裂纹，动态止滑系数平滑干式0.91湿式0.64，对大肠杆菌的抗菌率99.9％，对金黄色葡萄球菌的抗菌率99.6％，对大肠杆菌的抗菌率89.5％，防霉级别0级。
实施例3：
本实施例中，一种抗菌防霉橡胶鞋底的制备方法与实施例1中的制备方法相同，所不同的是配方原料中：
丁苯橡胶1502 25份、丙烯腈-丁二烯-苯乙烯三元共聚物2250 15份、白炭黑30份、矿物油15份、防霉剂A26 0.5份。
上述制备得到的抗菌防霉橡胶鞋底，密度1.20g/cm3，硬度65，DIN耐磨174mm3，撕裂强度71N/mm，氙灯老化试验无吐霜现象，臭氧老化试验无龟裂现象，耐折6万次无裂纹，动态止滑系数平滑干式0.80湿式0.51，对大肠杆菌的抗菌率99.4％，对金黄色葡萄球菌的抗菌率99.0％，对大肠杆菌的抗菌率87.7％，防霉级别1级。
实施例4：
本实施例中，一种抗菌防霉橡胶鞋底的制备方法与实施例1中的制备方法相同，所不同的是配方原料中：
溴化丁基橡胶2030 8份、氯化聚乙烯橡胶140A 5份、乙烯基苄基氯-甲基丙烯酸甲酯共聚物的三苯基膦盐抗菌剂3份、防霉剂A26 2份。
上述制备得到的抗菌防霉橡胶鞋底，密度1.08g/cm3，硬度62，DIN耐磨291mm3，撕裂强度70N/mm，氙灯老化试验无吐霜现象，臭氧老化试验无龟裂现象，耐折6万次无裂纹，动态止滑系数平滑干式0.76湿式0.49，对大肠杆菌的抗菌率99.1％，对金黄色葡萄球菌的抗菌率98.2％，对大肠杆菌的抗菌率86.2％，防霉级别0级。
对比例：
为了进一步的突出表明采用本发明技术方案的进步性，发明人制作了一个不添加抗菌剂和防霉剂的对比例，所述对比例中的橡胶鞋底的制备方法与实施例1中的制备方法相同，所不同的是配方原料中：抗菌剂0份、防霉剂0份。
对比例制备得到的橡胶鞋底，密度1.09g/cm3，硬度62，DIN耐磨179mm3，撕裂强度68N/mm，氙灯老化试验无吐霜现象，臭氧老化试验无龟裂现象，耐折6万次无裂纹，动态止滑系数平滑干式0.84湿式0.53，对大肠杆菌的抗菌率9.2％，对金黄色葡萄球菌的抗菌率8.3％，对大肠杆菌的抗菌率0％，防霉级别3级。
将上述实施例1～4和对比例的数据整理后，得到如下表1(注：硬度采用GS-706G硬度计测试，DIN耐磨按照GB/T 9867：2001测试，撕裂强度按照GB/T 10808-2006测试，氙灯老化试验采用氙灯老化试验箱Q-Sun Xe-1-S测试10天，臭氧老化试验采用臭氧试验机UA-2074测试2小时(臭氧浓度200ppm，温度60度)，耐折性能按照GB/T 3903.1-2008测试，动态止滑系数按照TM144：2011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测定抗菌率，霉菌试验与评价按照GJB 150《军用装备实验室环境试验方法》的第10部分进行)：
表1、实施例1-4和对比例的性能参数对照表
综上所述，按照本发明的抗菌防霉橡胶鞋底的制备方法，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％，对白色念珠菌的抗菌率超过85％的抗菌防霉橡胶鞋底，而且该鞋底具有良好的耐水耐候持效抗菌性能，防霉效果显著，而且具有较好的止滑耐磨性能，特别适合生产户外鞋、作训鞋。
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，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 (4)
1.一种抗菌防霉橡胶鞋底，其特征在于，由以下原料组成制得：
异戊橡胶 30 份
丁苯橡胶 20 - 25 份
丙烯腈-丁二烯-苯乙烯三元共聚物 15 - 20 份
溴化丁基橡胶 8 - 12 份
氯化聚乙烯橡胶 3 - 5 份
抗菌剂 3 - 8 份
白炭黑 20 - 30 份
矿物油 10 - 15 份
氧化锌 2 - 3 份
防老剂、 1 – 1.5 份
防霉剂 0.5 - 2 份
聚乙二醇 2 - 3 份
硅烷偶联剂 1 - 2 份
聚乙烯蜡 2 - 3 份
硫磺 2 - 3 份
硫化促进剂 2 - 3 份；
所述抗菌剂为高分子抗菌剂，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。
2.根据权利要求1所述的抗菌防霉橡胶鞋底，其特征在于，由组分按下列重量份原料制备而成:
异戊橡胶 30 份
丁苯橡胶 20 份
丙烯腈-丁二烯-苯乙烯三元共聚物 18 份
溴化丁基橡胶 10 份
氯化聚乙烯橡胶 4 份
抗菌剂 5 份
白炭黑 22 份
矿物油 10 份
氧化锌 2 份
防老剂 1 份
防霉剂 1 份
聚乙二醇 2 份
硅烷偶联剂 1.1 份
聚乙烯蜡 2 份
硫磺 2.2 份
硫化促进剂 2.2 份。
3.根据权利要求1所述抗菌防霉橡胶鞋底，其特征在于：所述丙烯腈-丁二烯-苯乙烯三元共聚物，其中丙烯腈含量大于18%、苯乙烯大于20%。
4.一种制备权利要求1-3任一所述抗菌防霉橡胶鞋底的制备方法，其特征在于：按照配方比例称量异戊橡胶、丁苯橡胶、丙烯腈-丁二烯-苯乙烯三元共聚物、溴化丁基橡胶、氯化聚乙烯橡胶、抗菌剂、白炭黑、矿物油、氧化锌、防老剂、防霉剂、聚乙二醇、硅烷偶联剂、聚乙烯蜡、硫磺、硫化促进剂，将组分材料除硫磺、硫化促进剂以外的原料放入密炼机中密炼，108-110摄氏度排胶，室温放置24小时，然后在双辊开炼机上混炼，并加入准确称量的硫磺、硫化促进剂，混炼均匀后，以均匀片状出片，最后将物料裁成鞋底形状放入橡胶鞋模中硫化成型，即得到抗菌防霉橡胶鞋底。
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