CN106977756A - 一种防霉抗菌涂布膜及其制备方法 - Google Patents
一种防霉抗菌涂布膜及其制备方法 Download PDFInfo
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Abstract
本发明公开的一种防霉抗菌涂布膜,包括基材、基材表面的涂料层、涂料层和基材之间的底胶层,所述涂料层是由改性丙烯酸涂料涂覆在基材表面并烘干后形成的涂层,所述的底胶层由斥水性树脂粘结剂构成。该防霉抗菌涂布膜具有优异的低温热封性能和较好的热封强度,并具有非常好的透明度和令人满意的光泽性能,且该防霉抗菌涂布膜能有效的达到防霉抗菌的效果。
Description
技术领域
本发明涉及涂布膜制备的技术领域,特别涉及一种防霉抗菌涂布膜及其制备方法。
背景技术
涂布膜在包装行业,尤其软包装行业,由于其优异的阻隔性能,其广阔的市场前景在国内与日俱增。同时,在日益增长的健康和卫生的意识下,人们对防霉抗菌性的材料,即在室内空间就显示出抗微生物活性和抗病毒活性的材料越来越重视。因此,包装行业急需开发一款具有防霉抗菌效果的涂布膜。
发明内容
本发明的目的是提供一种防霉抗菌涂布膜及其制备方法,解决上述现有技术问题中的一个或者多个。
本发明提供的一种防霉抗菌涂布膜,包括基材、基材表面的涂料层、涂料层和基材之间的底胶层,所述涂料层是由改性丙烯酸涂料涂覆在基材表面并烘干后形成的涂层,所述的底胶层由斥水性树脂粘结剂构成。
在一些实施方式中,基材为金属、玻璃、天然树脂、合成树脂、陶瓷、木材、纸、纤维、无纺布、织布或皮革中的一种或多种。
在一些实施方式中,斥水性树脂粘结剂为具有包含二甲基硅骨架的侧链,并且还具有氟烷基的丙烯酸树脂。
在一些实施方式中,丙烯酸涂料包括25-95质量份的改性丙烯酸乳液、0-70质量份的软水、2-15质量份的滑爽剂、0.1-5质量份的防黏剂。
在一些实施方式中,丙烯酸乳液由质量百分含量为10-80%的丙烯酸和90-20%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,所述滑爽剂为棕榈蜡,所述防黏剂为二氧化硅。
在一些实施方式中,丙烯酸乳液的改性方法,包括以下步骤:
α1、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的分散剂,得到光催化改性剂备用;
α2、将质量百分比为5-10%的上述光催化改性剂加入所述的丙烯酸乳液,同时用搅拌器不断搅拌。
在一些实施方式中,分散剂为聚烯丙基胺、聚乙烯基胺、聚脒、聚赖氨酸、聚鸟氨酸、聚精氨酸、聚组氨酸、海藻酸、淀粉、壳多糖、壳聚糖、果胶中的一种或多种。
在一些实施方式中,涂布膜的厚度为0.1-5μm,所述基材厚度为10-100μm。
一种防霉抗菌涂布膜的制备方法,包含以下步骤:
β1、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的分散剂,得到光催化改性剂备用;
β2、将质量百分比为5-10%的上述光催化改性剂加入由10-80%的丙烯酸和90-20%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,用搅拌器不断搅拌,得到改性丙烯酸乳液;
β3、将25-95质量份的改性丙烯酸乳液、0-70质量份的软水、2-15质量份的滑爽剂、0.1-5质量份的防黏剂加到反应罐中不断的搅拌,得到丙烯酸涂料;
β4、用刮棒涂布机在基材上涂覆底胶并烘干,所述烘干温度为90-140℃,烘干时间为5-20秒;用刮棒涂布机将所述丙烯酸涂料均匀涂布在底胶层上,所述丙烯酸涂料的涂布量为0.3-3.5g/m2,并通过在150℃温度下加热10min进行干燥,得到所述的防霉抗菌的涂布膜。
在一些实施方式中,二氧化钛的制备方法包括以下步骤:
γ1、将TiO2•nH2O和KOH二者摩尔比为0.4-0.6,加入适量的水,进行研磨,然后在马弗炉中升温至450-500°C后保温2h,慢冷至室温,得到中间相K6Ti2O7;
γ2、然后将分散好的中间产物K6Ti2O7投入到少量水中,放置1-2天,然后将所得的水合产物投入适量水中进行搅拌,不断滴加0.5mol /L的盐酸,用酸度计控制溶液的pH值为4.0-5.0;
γ3、待体系稳定达到平衡后抽滤出中间产物,用水洗至中性并干燥至恒重得到产物钛酸,然后在马弗炉中以10°C•min-1的速度烧结至700-800°C,保温2h,慢冷至室温,得到所述的微孔TiO2。
本发明中的涂布膜,采用特殊的丙烯酸涂料配方,使得这种丙烯酸涂布膜产品具有优异的低温热封性能和较好的热封强度,并具有非常好的透明度和令人满意的光泽性能。而合理的涂膜厚度,使得这种丙烯酸涂布膜具有优异的性价比和极低的涂布量,大大降低了制造成本。
在防霉抗菌方面,通过光催化材料的改性,能有效的达到光催化杀菌的效果。原理如下:微孔TiO2的电子结构特点为价带结构,且其带隙能宽,但是担载CuO能使得介孔TiO2的带隙变窄,而微孔TiO2由于其比表面积大能大量担载CuO,从而使得只要太阳光就能将电子从价带激发到导带,同时在价带产生相应的空穴,形成高活性的电子-空穴对,而CuO的存在能避免电子空穴复合,从而得到大量活性电子-空穴对,此时在表面就会发生氧化还原反应,空穴与表面吸附的H2O或OH-反应形成具有很强氧化性的活性羟基;电子则与表面吸附的氧分子反应,生成超氧离子。超氧离子可与水进一步反应,生成过羟基和双氧水,这些物质能与生物大分子如脂类、蛋白质、酶类以及核酸大分子反应,直接损害或通过一系列氧化链式反应,而对生物细胞结构引起广泛的损伤性怕坏,以达到防霉的效果。
具体实施方式
下面通过实施方式对本发明进行进一步详细的说明。
实施案例1:
a1、将TiO2•nH2O和KOH二者摩尔比为0.4,加入适量的水,进行研磨,然后在马弗炉中升温至450°C后保温2h,慢冷至室温,得到中间相K6Ti2O7;
a2、然后将分散好的中间产物K6Ti2O7投入到少量水中,放置1天,然后将所得的水合产物投入适量水中进行搅拌,不断滴加0.5mol /L的盐酸,用酸度计控制溶液的pH值为4.0;
a3、待体系稳定达到平衡后抽滤出中间产物,用水洗至中性并干燥至恒重得到产物钛酸,然后在马弗炉中以10°C•min-1的速度烧结至700°C,保温2h,慢冷至室温,得到所述的微孔TiO2;
a4、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的聚烯丙基胺,得到光催化改性剂备用;
a5、将质量百分比为5%的上述光催化改性剂加入由10%的丙烯酸和90%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,用搅拌器不断搅拌,得到改性丙烯酸乳液;
a6、将25质量份的改性丙烯酸乳液、0质量份的软水、2质量份的滑爽剂、0.1质量份的防黏剂加到反应罐中不断的搅拌,得到丙烯酸涂料;
a7、用刮棒涂布机在合成树脂上涂覆底胶并烘干, 上述底胶为具有包含二甲基硅骨架的侧链,并且还具有氟烷基的丙烯酸树脂,所述烘干温度为90℃,烘干时间为5秒;用刮棒涂布机将所述丙烯酸涂料均匀涂布在底胶层上,所述丙烯酸涂料的涂布量为0.3g/m2,并通过在150℃温度下加热10min进行干燥,得到所述的防霉抗菌的涂布膜a。
实施案例2:
b1、将TiO2•nH2O和KOH二者摩尔比为0.6,加入适量的水,进行研磨,然后在马弗炉中升温至500°C后保温2h,慢冷至室温,得到中间相K6Ti2O7;
b2、然后将分散好的中间产物K6Ti2O7投入到少量水中,放置2天,然后将所得的水合产物投入适量水中进行搅拌,不断滴加0.5mol /L的盐酸,用酸度计控制溶液的pH值为5.0;
b3、待体系稳定达到平衡后抽滤出中间产物,用水洗至中性并干燥至恒重得到产物钛酸,然后在马弗炉中以10°C•min-1的速度烧结至800°C,保温2h,慢冷至室温,得到所述的微孔TiO2;
b4、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的聚乙烯基胺,得到光催化改性剂备用;
b5、将质量百分比为10%的上述光催化改性剂加入由80%的丙烯酸和90-20%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,用搅拌器不断搅拌,得到改性丙烯酸乳液;
b6、将95质量份的改性丙烯酸乳液、70质量份的软水、15质量份的滑爽剂、5质量份的防黏剂加到反应罐中不断的搅拌,得到丙烯酸涂料;
b7、用刮棒涂布机在无纺布上涂覆底胶并烘干, 上述底胶为具有包含二甲基硅骨架的侧链,并且还具有氟烷基的丙烯酸树脂,所述烘干温度为140℃,烘干时间为20秒;用刮棒涂布机将所述丙烯酸涂料均匀涂布在底胶层上,所述丙烯酸涂料的涂布量为3.5g/m2,并通过在150℃温度下加热10min进行干燥,得到所述的防霉抗菌的涂布膜b。
实施案例3:
c1、将TiO2•nH2O和KOH二者摩尔比为0.5,加入适量的水,进行研磨,然后在马弗炉中升温至480°C后保温2h,慢冷至室温,得到中间相K6Ti2O7;
c2、然后将分散好的中间产物K6Ti2O7投入到少量水中,放置1.5天,然后将所得的水合产物投入适量水中进行搅拌,不断滴加0.5mol /L的盐酸,用酸度计控制溶液的pH值为4.5;
c3、待体系稳定达到平衡后抽滤出中间产物,用水洗至中性并干燥至恒重得到产物钛酸,然后在马弗炉中以10°C•min-1的速度烧结至750°C,保温2h,慢冷至室温,得到所述的微孔TiO2;
c4、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的海藻酸,得到光催化改性剂备用;
c5、将质量百分比为8%的上述光催化改性剂加入由30%的丙烯酸和70%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,用搅拌器不断搅拌,得到改性丙烯酸乳液;
c6、将30质量份的改性丙烯酸乳液、35质量份的软水、8质量份的滑爽剂、2质量份的防黏剂加到反应罐中不断的搅拌,得到丙烯酸涂料;
c7、用刮棒涂布机在玻璃上涂覆底胶并烘干, 上述底胶为具有包含二甲基硅骨架的侧链,并且还具有氟烷基的丙烯酸树脂,所述烘干温度为100℃,烘干时间为15秒;用刮棒涂布机将所述丙烯酸涂料均匀涂布在底胶层上,所述丙烯酸涂料的涂布量为2g/m2,并通过在150℃温度下加热10min进行干燥,得到所述的防霉抗菌的涂布膜c。
将实施案例得到的防霉抗涂布膜进行防霉测试。
(1)抗微生物活性的评估。
根据JIS R1702,使用大肠杆菌评估各涂布膜的抗微生物活性,辐射条件为10001x(荧光灯,经过4小时)。根据公式计算抗微生物活性R(抗微生物);
R(抗微生物)=Log(B/C);
其中R(抗微生物):在辐射条件下涂布膜的抗微生物活性;
B:在辐射条件下用光辐射之后基板上的活细胞计数;
C:在辐射条件下用光辐射之后涂布膜上的活细胞计数。
由上表所述,防霉抗菌涂布膜显示出较高的抗微生物活性,说明涂布膜的防霉抗菌效果好。
(2)防霉实验。
混合霉菌液喷至涂布膜a,b,c表面,然后将试板悬挂在4-20℃的高湿度箱中28天,用肉眼和显微镜观察涂料表面的发霉情况。
根据BS 3900-G6标准,霉菌/藻类繁殖率分为6级,即0为无滋生,1为滋生面积小于1%,2为滋生面积为1-10%,3为滋生面积为11-30%,4为滋生面积为31-70%,5为滋生面积大于70%。密度划分为:0为无滋生,A为极微,B为轻度,C为中度,D为密集。
从上述防霉测试中,可以发现实施案例得到的防霉涂布膜能有效的达到防霉抗菌的效果。
以上表述仅为本发明的优选方式,应当指出,对本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干变形和改进,这些也应视为发明的保护范围之内。
Claims (10)
1.一种防霉抗菌涂布膜,其特征在于,包括基材、基材表面的涂料层、涂料层和基材之间的底胶层,所述涂料层是由改性丙烯酸涂料涂覆在基材表面并烘干后形成的涂层,所述的底胶层由斥水性树脂粘结剂构成。
2.根据权利要求1所述的一种防霉抗菌涂布膜,其特征在于,所述基材为金属、玻璃、天然树脂、合成树脂、陶瓷、木材、纸、纤维、无纺布、织布或皮革中的一种或多种。
3.根据权利要求1所述的一种防霉抗菌涂布膜,其特征在于,所述斥水性树脂粘结剂为具有包含二甲基硅骨架的侧链,并且还具有氟烷基的丙烯酸树脂。
4.根据权利要求1所述的一种防霉抗菌涂布膜,其特征在于,所述丙烯酸涂料包括25-95质量份的改性丙烯酸乳液、0-70质量份的软水、2-15质量份的滑爽剂、0.1-5质量份的防黏剂。
5.根据权利要求4所述的一种防霉抗菌涂布膜,其特征在于,所述丙烯酸乳液由质量百分含量为10-80%的丙烯酸和90-20%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,所述滑爽剂为棕榈蜡,所述防黏剂为二氧化硅。
6.根据权利要求5所述的一种防霉抗菌涂布膜,其特征在于,所述丙烯酸乳液的改性方法,包括以下步骤:
α1、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的分散剂,得到光催化改性剂备用;
α2、将质量百分比为5-10%的上述光催化改性剂加入所述的丙烯酸乳液,同时用搅拌器不断搅拌。
7.根据权利要求6所述的一种防霉抗菌涂布膜,其特征在于,所述分散剂为聚烯丙基胺、聚乙烯基胺、聚脒、聚赖氨酸、聚鸟氨酸、聚精氨酸、聚组氨酸、海藻酸、淀粉、壳多糖、壳聚糖、果胶中的一种或多种。
8.根据权利要求1所述的一种防霉抗菌涂布膜,其特征在于,所述涂布膜的厚度为0.1-5μm,所述基材厚度为10-100μm。
9.一种防霉抗菌涂布膜的制备方法,其特征在于,包含以下步骤:
β1、将20质量份的微孔二氧化钛和1质量份的氧化铜,加至84质量份的甲基乙基酮中得到悬浮液,将该悬浮液在90℃下加热1h,同时用搅拌器搅拌加入100质量份的分散剂,得到光催化改性剂备用;
β2、将质量百分比为5-10%的上述光催化改性剂加入由10-80%的丙烯酸和90-20%的丙烯酸甲酯或丙烯酸乙酯的共聚物形成的乳液,用搅拌器不断搅拌,得到改性丙烯酸乳液;
β3、将25-95质量份的改性丙烯酸乳液、0-70质量份的软水、2-15质量份的滑爽剂、0.1-5质量份的防黏剂加到反应罐中不断的搅拌,得到丙烯酸涂料;
β4、用刮棒涂布机在基材上涂覆底胶并烘干,所述烘干温度为90-140℃,烘干时间为5-20秒;用刮棒涂布机将所述丙烯酸涂料均匀涂布在底胶层上,所述丙烯酸涂料的涂布量为0.3-3.5g/m2,并通过在150℃温度下加热10min进行干燥,得到所述的防霉抗菌的涂布膜。
10.根据权利要求9所述的一种防霉抗菌涂布膜的制备方法,其特征在于,所述的二氧化钛的制备方法包括以下步骤:
γ1、将TiO2•nH2O和KOH二者摩尔比为0.4-0.6,加入适量的水,进行研磨,然后在马弗炉中升温至450-500°C后保温2h,慢冷至室温,得到中间相K6Ti2O7;
γ2、然后将分散好的中间产物K6Ti2O7投入到少量水中,放置1-2天,然后将所得的水合产物投入适量水中进行搅拌,不断滴加0.5mol /L的盐酸,用酸度计控制溶液的pH值为4.0-5.0;
γ3、待体系稳定达到平衡后抽滤出中间产物,用水洗至中性并干燥至恒重得到产物钛酸,然后在马弗炉中以10°C•min-1的速度烧结至700-800°C,保温2h,慢冷至室温,得到所述的微孔TiO2。
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