CN116716745B - 多层涂饰抗菌型皮革 - Google Patents
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Abstract
本发明涉及制革技术领域,具体公开一种多层涂饰抗菌型皮革,中涂层采用包括色粉、环氧聚硅氧烷丙烯酸树脂乳液和水的涂料组合物涂布固化形成;顶涂层采用涂饰组合物涂布固化形成,涂饰组合物包括碳量子点/壳聚糖基改性酪素、乳化剂、水、色膏;碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:柠檬酸水溶液、酪素和烷基化壳聚糖。本发明创新性地借助碳量子点具有的丰富含氧基团如环氧基作为中间点将酪素接枝在壳聚糖上,实现抗菌性能的同时降低了酪素分子间相互作用力而达到增塑效果,成膜柔软连续,改善成膜性差和成膜硬脆缺陷。
Description
技术领域
本发明涉及制革技术领域,具体涉及一种多层涂饰抗菌型皮革。
背景技术
酪素是应用较为广泛的一种水溶性成膜剂,其由牛奶中提取,本质为一种复合蛋白质,环保安全,符合目前市面上对环保型产品的需求。过去酪素一直被用于皮革涂饰,缘于其与皮革粘合力强,所形成的薄膜耐温性好,更为重要的是,酪素薄膜具有优异的透气透水性,这是很多涂料所不具备的。但是,酪素作为皮革涂饰剂用成膜剂仍存在成膜较硬脆以及成膜性差、薄膜不连续的缺点。
为此,中国公开专利文献(CN110527110A)公开了一种酪素改性方法,包括以下步骤:a.引发剂溶液的制备;b.单体溶液的制备;c.酪素溶液的制备;d.酪素的改性;其中单体溶液包括环硅氧烷和酰胺化合物;该改性方法制备得到的改性酪素成膜后既透水透气,还保证了湿擦后的固色效果,且薄膜具有良好的柔韧性,改善了酪素自身成膜硬脆的问题。但是该技术并不能够同时赋予酪素成膜层兼具皮革表面的抗菌性能。
发明内容
鉴于现有技术的不足,本发明所要解决的技术问题是提供一种多层涂饰抗菌型皮革,改善酪素成膜剂的成膜硬脆缺陷并赋予良好的抗菌性能。
为实现上述发明目的,本发明采用的技术方案是:
多层涂饰抗菌型皮革,包括底涂层、中涂层和顶涂层,所述中涂层采用包括色粉、环氧聚硅氧烷丙烯酸树脂乳液和水的涂料组合物涂布固化形成;所述顶涂层采用涂饰组合物涂布固化形成,该涂饰组合物包括如下重量份数的组分:60-100份碳量子点/壳聚糖基改性酪素、5-10份乳化剂、100份水、0-20份色膏;所述碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:140-150的柠檬酸水溶液、45-50份酪素和2-5份烷基化壳聚糖。
优选地,所述碳量子点/壳聚糖基改性酪素的制备方法包括如下步骤:
S1、取100份柠檬酸水溶液,于200℃~230℃温度下加热反应5h~8h,接着冷却、离心得到碳量子点溶液;
S2、往步骤S1的碳量子点溶液中加入所述重量份数的酪素,于70℃~80℃温度下搅拌至酪素完全溶解,亲核加成反应得到碳量子点改性酪素溶液,冷却;
S3、取剩下的柠檬酸水溶液与所述重量份数的烷基化壳聚糖混合搅拌,加入脱水剂进行脱水缩合反应,干燥得到柠檬酸-烷基化壳聚糖;
S4、往步骤S2的碳量子点改性酪素溶液中加入步骤S3的柠檬酸-烷基化壳聚糖,于70℃~80℃温度下搅拌进行亲核加成反应;
S5、反应结束后溶于盐酸和DMSO的混合溶液中,超声20min-40min,然后透析、离心得到自组装为纳米胶束形态的碳量子点/壳聚糖基改性酪素。
优选地,所述盐酸和DMSO的体积比为3∶7。
优选地,所述柠檬酸水溶液的质量分数为5%-10%。
优选地,所述脱水剂为EDC。
优选地,所述底涂层由色料、阳离子丙烯酸树脂、阳离子蜡剂、渗透剂和水组成。
优选地,所述顶涂层还包括手感剂和/或光亮剂。
本发明顶层涂饰组合物主料采用碳量子点/壳聚糖基改性酪素,由于酪素含有的官能基团为伯氨基、亚胺基及羧基,而具有抗菌性能的壳聚糖含有的官能基团主要为伯氨基和仲胺基,现有技术中一般不考虑利用壳聚糖对酪素进行改性,而本发明创新性地借助碳量子点具有的丰富含氧基团如环氧基作为中间点将酪素接枝在壳聚糖上,实现抗菌性能的同时降低了酪素分子间相互作用力而达到增塑效果,成膜柔软连续,改善成膜性差和成膜硬脆缺陷。本发明采用脱水缩合法在烷基化壳聚糖上形成了同时具有烷基疏水链和柠檬酸亲水链的两性聚合物,从而实现自组装形成核壳结构纳米胶束,在烘干蒸发水分时产生堆积、凝聚、融合和扩散,继而实现连续性成膜;另外,碳量子点/壳聚糖基改性酪素作为顶涂层主料,其分子链中的伯氨基在烘干时还可以与中涂层的环氧聚硅氧烷丙烯酸树脂中的环氧基反应结合,利于增强顶涂层和中涂层的剥离强度,耐候性好,进一步避免热粘冷脆。
具体实施方式
实施例1
本实施例提供一种多层涂饰抗菌型皮革,包括底涂层、中涂层和顶涂层。
本实施例的底涂层采用喷涂工艺将涂料组合物A喷涂在皮料表面,喷枪转动速度16r/min,传送带速度10r/min,雾化压力0.35MPa,底涂层厚度为65μm。所述涂料组合物A由10份色料、85份阳离子丙烯酸树脂、45份阳离子蜡剂、15份渗透剂和100份水组成,烘干固化温度为95℃。烘干后静置3小时后上滚光机滚光处理,温度105℃,压力5MPa。
本实施例的中涂层采用喷涂工艺将涂料组合物B喷涂在底涂层表面,喷枪转动速度16r/min,传送带速度10r/min,雾化压力0.6MPa,中涂层厚度为40μm。所述涂料组合物B由15份色粉、70份环氧聚硅氧烷丙烯酸树脂乳液和100份水组成,烘干固化温度为95℃。
本实施例的顶涂层采用辊涂工艺将涂饰组合物辊涂在中涂层表面,烘干固化温度为95℃,顶涂层厚度70μm。所述涂饰组合物由100份碳量子点/壳聚糖基改性酪素、10份乳化剂吐温20、100份水、5份色膏、10份手感剂7615-AT组成。
所述碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:140份质量分数为10%的柠檬酸水溶液、45份酪素和3份烷基化壳聚糖。所述碳量子点/壳聚糖基改性酪素的制备方法包括如下步骤:S1、取100份柠檬酸水溶液,于230℃温度下加热反应6h,接着冷却、离心得到碳量子点溶液;S2、往步骤S1的碳量子点溶液中加入所述重量份数的酪素,于80℃温度下搅拌至酪素完全溶解,在该80℃温度下亲核加成反应得到碳量子点改性酪素溶液,冷却;S3、取剩下的柠檬酸水溶液与所述重量份数的烷基化壳聚糖混合搅拌,加入脱水剂EDC进行脱水缩合反应,干燥得到柠檬酸-烷基化壳聚糖;S4、往步骤S2的碳量子点改性酪素溶液中加入步骤S3的柠檬酸-烷基化壳聚糖,于80℃温度下搅拌进行亲核加成反应;S5、反应结束后溶于盐酸和DMSO的混合溶液中,盐酸和DMSO的体积比为3∶7,超声30min,然后透析、离心得到自组装为纳米胶束形态的碳量子点/壳聚糖基改性酪素。
实施例2
本实施例提供一种多层涂饰抗菌型皮革,包括底涂层、中涂层和顶涂层。
本实施例的底涂层采用喷涂工艺将涂料组合物A喷涂在皮料表面,喷枪转动速度16r/min,传送带速度10r/min,雾化压力0.35MPa,底涂层厚度为80μm。所述涂料组合物A由15份色料、90份阳离子丙烯酸树脂、40份阳离子蜡剂、20份渗透剂和100份水组成,烘干固化温度为90℃。烘干后静置3小时后上滚光机滚光处理,温度105℃,压力5MPa。
本实施例的中涂层采用喷涂工艺将涂料组合物B喷涂在底涂层表面,喷枪转动速度16r/min,传送带速度10r/min,雾化压力0.6MPa,中涂层厚度为50μm。所述涂料组合物B由20份色粉、80份环氧聚硅氧烷丙烯酸树脂乳液和100份水组成,烘干固化温度为90℃。
本实施例的顶涂层采用辊涂工艺将涂饰组合物辊涂在中涂层表面,烘干固化温度为90℃,顶涂层厚度60μm。所述涂饰组合物由90份碳量子点/壳聚糖基改性酪素、10份乳化剂吐温20、100份水、15份色膏、8份手感剂7615-AT、5份光亮剂6190-LA组成。
所述碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:150份质量分数为5%的柠檬酸水溶液、50份酪素和5份烷基化壳聚糖。所述碳量子点/壳聚糖基改性酪素的制备方法包括如下步骤:S1、取100份柠檬酸水溶液,于230℃温度下加热反应6h,接着冷却、离心得到碳量子点溶液;S2、往步骤S1的碳量子点溶液中加入所述重量份数的酪素,于80℃温度下搅拌至酪素完全溶解,在该80℃温度下亲核加成反应得到碳量子点改性酪素溶液,冷却;S3、取剩下的柠檬酸水溶液与所述重量份数的烷基化壳聚糖混合搅拌,加入脱水剂EDC进行脱水缩合反应,干燥得到柠檬酸-烷基化壳聚糖;S4、往步骤S2的碳量子点改性酪素溶液中加入步骤S3的柠檬酸-烷基化壳聚糖,于80℃温度下搅拌进行亲核加成反应;S5、反应结束后溶于盐酸和DMSO的混合溶液中,盐酸和DMSO的体积比为3∶7,超声30min,然后透析、离心得到自组装为纳米胶束形态的碳量子点/壳聚糖基改性酪素。
实施例3
本实施例提供一种多层涂饰抗菌型皮革,包括底涂层、中涂层和顶涂层。
本实施例的底涂层采用喷涂工艺将涂料组合物A喷涂在皮料表面,喷枪转动速度17r/min,传送带速度10r/min,雾化压力0.38MPa,底涂层厚度为60μm。所述涂料组合物A由12份色料、80份阳离子丙烯酸树脂、50份阳离子蜡剂、18份渗透剂和100份水组成,烘干固化温度为95℃。烘干后静置3小时后上滚光机滚光处理,温度105℃,压力5MPa。
本实施例的中涂层采用喷涂工艺将涂料组合物B喷涂在底涂层表面,喷枪转动速度16r/min,传送带速度8r/min,雾化压力0.6MPa,中涂层厚度为45μm。所述涂料组合物B由10份色粉、75份环氧聚硅氧烷丙烯酸树脂乳液和100份水组成,烘干固化温度为90℃。
本实施例的顶涂层采用辊涂工艺将涂饰组合物辊涂在中涂层表面,烘干固化温度为90℃,顶涂层厚度80μm。所述涂饰组合物由80份碳量子点/壳聚糖基改性酪素、8份乳化剂吐温20、100份水、10份色膏、5份手感剂7615-AT组成。
所述碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:145份质量分数为8%的柠檬酸水溶液、50份酪素和2份烷基化壳聚糖。所述碳量子点/壳聚糖基改性酪素的制备方法包括如下步骤:S1、取100份柠檬酸水溶液,于220℃温度下加热反应8h,接着冷却、离心得到碳量子点溶液;S2、往步骤S1的碳量子点溶液中加入所述重量份数的酪素,于80℃温度下搅拌至酪素完全溶解,在该80℃温度下亲核加成反应得到碳量子点改性酪素溶液,冷却;S3、取剩下的柠檬酸水溶液与所述重量份数的烷基化壳聚糖混合搅拌,加入脱水剂EDC进行脱水缩合反应,干燥得到柠檬酸-烷基化壳聚糖;S4、往步骤S2的碳量子点改性酪素溶液中加入步骤S3的柠檬酸-烷基化壳聚糖,于80℃温度下搅拌进行亲核加成反应;S5、反应结束后溶于盐酸和DMSO的混合溶液中,盐酸和DMSO的体积比为3∶7,超声30min,然后透析、离心得到自组装为纳米胶束形态的碳量子点/壳聚糖基改性酪素。
分别取上述实施例1-3制得的多层涂饰抗菌性皮革按照ASTM D751测试剥离强度均达8.8-9.3N/mm,按照QB/T 4870-2015测试G56柔软度均在4.7-5.0级,按照GB/T31402-2015测试能99%灭除表面大肠杆菌、金黄色葡萄球菌、白色念珠菌。
以上显示和描述了本发明创造的基本原理和主要特征及本发明的优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明创造精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内,本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (6)
1.多层涂饰抗菌型皮革,包括底涂层、中涂层和顶涂层,其特征在于:
所述中涂层采用包括色粉、环氧聚硅氧烷丙烯酸树脂乳液和水的涂料组合物涂布固化形成;
所述顶涂层采用涂饰组合物涂布固化形成,该涂饰组合物包括如下重量份数的组分:60-100份碳量子点/壳聚糖基改性酪素、5-10份乳化剂、100份水、0-20份色膏;所述碳量子点/壳聚糖基改性酪素由如下重量份数组分反应而成:140-150的柠檬酸水溶液、45-50份酪素和2-5份烷基化壳聚糖;
所述碳量子点/壳聚糖基改性酪素的制备方法包括如下步骤:
S1、取100份柠檬酸水溶液,于200℃~230℃温度下加热反应5h~8h,接着冷却、离心得到碳量子点溶液;
S2、往步骤S1的碳量子点溶液中加入所述重量份数的酪素,于70℃~80℃温度下搅拌至酪素完全溶解,亲核加成反应得到碳量子点改性酪素溶液,冷却;
S3、取剩下的柠檬酸水溶液与所述重量份数的烷基化壳聚糖混合搅拌,加入脱水剂进行脱水缩合反应,干燥得到柠檬酸-烷基化壳聚糖;
S4、往步骤S2的碳量子点改性酪素溶液中加入步骤S3的柠檬酸-烷基化壳聚糖,于70℃~80℃温度下搅拌进行亲核加成反应;
S5、反应结束后溶于盐酸和DMSO的混合溶液中,超声20min-40min,然后透析、离心得到自组装为纳米胶束形态的碳量子点/壳聚糖基改性酪素。
2.根据权利要求1所述的多层涂饰抗菌型皮革,其特征在于:所述盐酸和DMSO的体积比为3∶7。
3.根据权利要求1所述的多层涂饰抗菌型皮革,其特征在于:所述柠檬酸水溶液的质量分数为5%-10%。
4.根据权利要求1所述的多层涂饰抗菌型皮革,其特征在于:所述脱水剂为EDC。
5.根据权利要求1所述的多层涂饰抗菌型皮革,其特征在于:所述底涂层由色料、阳离子丙烯酸树脂、阳离子蜡剂、渗透剂和水组成。
6.根据权利要求1所述的多层涂饰抗菌型皮革,其特征在于:所述顶涂层还包括手感剂和/或光亮剂。
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