CN106476380B - 一种缓释型二氧化氯抗菌膜的制备工艺 - Google Patents

一种缓释型二氧化氯抗菌膜的制备工艺 Download PDF

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CN106476380B
CN106476380B CN201610869975.7A CN201610869975A CN106476380B CN 106476380 B CN106476380 B CN 106476380B CN 201610869975 A CN201610869975 A CN 201610869975A CN 106476380 B CN106476380 B CN 106476380B
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黄崇杏
李志嘉
李翠翠
张保东
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Abstract

本发明公开了一种缓释型二氧化氯抗菌膜的制备工艺。它以聚乙烯醇和聚乳酸为主要基材，采用湿法复合将A膜和B膜复合在一起，制备了反应型二氧化氯抗菌膜。A膜选用聚乙烯醇为成膜基材，用稳定性二氧化氯水溶液配制成聚乙烯醇凝胶水溶液，再经流延工艺烘干成膜，并使用甘油作增塑剂，添加羧甲基纤维素以增加薄膜的吸湿性，促进二氧化氯的释放。B膜选用聚乳酸为成膜基材，用二氯甲烷溶解聚乳酸，向其中加入活化剂柠檬酸或酒石酸的一种。添加增塑剂、抗氧化剂后流延成膜。制备得到的二氧化氯抗菌膜需要水分来激活，所以可以作为水分含量高的果蔬的包装材料，果蔬呼吸作用释放的水分激活了二氧化氯抗菌剂，在降低了包装内水分的同时又抑制了微生物的生长，从而延长了果蔬的货架期。

Description

一种缓释型二氧化氯抗菌膜的制备工艺
技术领域
本发明涉及一种包装材料的制备工艺，具体地说是一种缓释型二氧化氯抗菌膜的制备工艺。
技术背景
生鲜食品主要是指果蔬、水产品和新鲜的肉类，由于生鲜食品具有季节性、区域性以及不耐储藏等特点，与消费者对食品丰富多样和高品质品的需求相矛盾，所以为了满足消费者的需求，我们就要大力发展保鲜技术。根据生鲜食品自身的新陈代谢以及温度、湿度、PH和微生物等环境因素的影响，生鲜食品的保鲜技术大致分为物理保鲜、化学保鲜和生物保鲜。物理保鲜技术大致有低温冷藏、冷冻、瞬时高温、真空包装、气调包装等；化学保鲜技术主要是向食品或包装材料中添加化学药剂，常用的保鲜剂有：有机酸类保鲜剂、乙醇保鲜剂、二氧化氯消毒剂、乙烯抑制剂与吸收剂、壳聚糖、天然防腐剂、纳米银等；生物保鲜技术主要有转基因技术、抑制病害的发生和转移等。二氧化氯以其广谱性、高效、受温度影响小、pH适用范围广、安全无残留、对人体无刺激等优点成为国际上公认的安全、无毒的绿色消毒剂。而目前二氧化氯作为抗菌剂使用的主要方式有粉末投放、浸渍涂敷、缓释衬垫、抗菌薄膜等形式。
CN104719335A发明了一种涉及环境净化领域的二氧化氯可控缓释制剂，包含缓释载体和二氧化氯前体物；缓释载体包含缓释剂、增稠剂、活化剂和水余量。将二氧化氯前体物放置在缓释载体内部，直接放置于环境，其缓慢放出来的二氧化氯可降低环境中的甲醛、苯等污染物。
殷豪章发明了一种二氧化氯水凝胶的制备方法，包括制备聚乙二醇共聚物、双-癸基十四烷醇水溶液的步骤；制备聚乙二醇共聚物、双-癸基十四烷醇胶合物的步骤；二氧化氯水溶液的制备步骤；将二氧化氯水溶液与胶合物均与混合制备二氧化氯凝胶的步骤。
华侨大学发明了一种遇水敏感性、高效抗菌复合膜的制备方法，其采用天然精油和缓释型二氧化氯做抗菌剂，采用多层共挤的方法制备抗菌薄膜。但其所用的亚氯酸钠、次氯酸钠或氯酸钠具有热不稳定性，在造粒和吹膜的过程中如果温度控制不当具有潜在的危险性。
北京印刷学院发明了一种保鲜复合薄膜，其由高透气性流延聚乙烯外膜、乙烯-醋酸乙烯共聚物改性高透气性流延聚乙烯内膜，通过含二氧化氯释放粉末的粘合剂干法复合制备得到。此工艺制备的薄膜将二氧化氯释放粉末夹在了中间阻碍了其与水分的接触不利于二氧化氯释放粉末的激活，同时该膜据采用高透气性的设计不利于其包装食品风味的保持。
发明内容
本发明所要解决的技术问题是提供一种缓释型二氧化氯抗菌膜的制备工艺，使制得二氧化氯抗菌膜可降解，并可释放出二氧化氯抗菌剂，为绿色包装抗菌薄膜。
本发明以如下技术方案解决上述技术问题：
该制备工艺是采用湿法复合将A膜和B膜复合在一起制成以聚乳酸为基材的缓释型二氧化氯抗菌膜；
所述A膜的制备工艺是：选用水凝胶聚乙烯醇作为成膜基材，用稳定性二氧化氯水溶液配制成聚乙烯醇凝胶水溶液，再经流延工艺烘干成膜；
所述B膜的制备工艺是：选用聚乳酸作为成膜基材，用二氯甲烷溶解聚乳酸，并向其中加入二氧化氯的活化剂柠檬酸或酒石酸，添加增塑剂柠檬酸三丁酯或亚磷酸三苯酯，添加抗氧化剂丁基羟基茴香醚或叔丁基对苯二酚；
A膜和B膜复合时采用低密度聚乙烯或乙烯-醋酸乙烯共聚物为粘合剂，粘合剂用量为B膜质量的10％～50％。
A膜制备工艺中，所述稳定性二氧化氯水溶液的浓度为40ppm-37000ppm，配成的聚乙烯醇凝胶水溶液中聚乙烯醇的质量浓度为1％～10％。
A膜制备工艺中，配制聚乙烯醇凝胶水溶液时，在聚乙烯醇凝胶水溶液中添加甘油做增塑剂，添加羧甲基纤维素以增加薄膜的吸湿性，促进二氧化氯的释放，添加的甘油量为水凝胶聚乙烯醇质量的2％～52％，添加的羧甲基纤维素的质量与稳定性二氧化氯水溶液的体积比为0.1～2g:100ml。
A膜制备工艺中，配制聚乙烯醇凝胶水溶液时，按配制先将40％的稳定性二氧化氯水溶液与水凝胶聚乙烯醇混合，用电动搅拌机边倒边搅拌先溶胀，等到没有白色的团块时加入余量的稳定性二氧化氯水溶液。
所述B膜的制备工艺中，活化剂的添加量为聚乳酸质量的1％～20％；增塑剂的添加量为聚乳酸质量的5％～25％；抗氧化剂的添加量为聚乳酸质量的0.1％～1％。
所述B膜的制备工艺中，用二氯甲烷溶解聚乳酸时，聚乳酸的质量与二氯甲烷的体积比为4～10g:100ml。
本发明缓释型二氧化氯抗菌膜的制备工艺具有如下有益效果：
1.本发明制备工艺中采用的聚乙烯醇和聚乳酸都是可降解的包装材料，同时利用聚乙烯醇的吸湿性来吸收水分进而活化释放出二氧化氯，以及加入羧甲基纤维素钠来提高A膜的再溶胀性和对PH的敏感性，进而调节二氧化氯的释放速率。
2.本发明制备工艺中采用溶剂流延可使抗菌剂、活化剂等添加剂与成膜基材混合的更加均匀。
3.采用本发明工艺制备得到的缓释型二氧化氯抗菌膜中二氧化氯的保留量为10ppm～150000ppm，薄膜的拉伸强度为0.1MPa～100MPa，薄膜的厚度为0.1mm～1mm，抗菌率在70％以上。
4.本发明制备得到的二氧化氯抗菌膜需要水分来激活，所以可以作为水分含量高的果蔬的包装材料，果蔬呼吸作用释放的水分激活了二氧化氯抗菌剂，在降低了包装内水分的同时又抑制了微生物的生长，从而延长了果蔬的货架期。
具体实施方式
以下实例是用来更好的说明本发明，但本发明的保护范围不限于以下实例：
实施例1
制备A膜：称量8.0129gPVA溶于40ml浓度为36779.3ppm的稳定性二氧化氯水溶液，用电动搅拌机边倒边搅拌先溶胀，等到没有白色的团块时加入60ml浓度为36779.3ppm的稳定性二氧化氯水溶液，再依次加入2.0121g甘油和2.0074g羧甲基纤维素钠，同样用电动搅拌机边倒边搅拌，配制成一定浓度的PVA凝胶水溶液，搅拌均匀后再经AFA-II自动涂膜机流延成膜，放在40℃、RH45％环境下24h烘干制成A膜。该膜的二氧化氯保留量为124.0359mg/g，厚度为0.662mm，拉伸强度为1.86MPa。
制备B膜：称量10.009gPLA溶于100ml二氯甲烷，再依次加入2.0104g柠檬酸、0.5106g柠檬酸三丁酯和0.0105g丁基羟基茴香醚，用电动搅拌机混合均匀后流延成膜，再放在通风橱内12h。该薄膜的厚度为0.026mm，拉伸强度为40.74MPa。
制备缓释型二氧化氯抗菌膜：用AFA-II自动涂膜机在干燥后的A膜上涂布一层胶粘剂低密度聚乙烯，此时低密度聚乙烯用量为B膜质量的10％，再用涂膜机将B膜复合，制成以聚乳酸为基材的缓释型二氧化氯抗菌膜。得到的缓释型二氧化氯抗菌膜厚度为0.695mm，拉伸强度为42.12MPa，二氧化氯的保留量为99.2287mg/g。在40℃，RH60％的环境下，15天后二氧化氯的保留量为10.5238ppm。在37℃下，薄膜对大肠杆菌和金色葡萄球菌的抑菌率都在90％以上。
实施例2
A膜：称量4.0086g聚乙烯醇溶于40ml浓度为4082.1ppm的稳定性二氧化氯水溶液，用电动搅拌机边倒边搅拌先溶胀，等到没有白色的团块时再加入60ml浓度为4082.1ppm的稳定性二氧化氯水溶液，再依次加入0.0804g甘油和0.5024g羧甲基纤维素，同样用电动搅拌机边倒边搅拌，配制成一定浓度的聚乙烯醇凝胶水溶液，搅拌均匀后再经AFA-II自动涂膜机流延成膜，放在40℃、RH45％环境下24h烘干。制成薄膜的二氧化氯保留量为54.9743mg/g，厚度为0.259mm，拉伸强度为7.09MPa。
B膜：称量7.0109g聚乳酸溶于100ml二氯甲烷，再依次加入0.7014g柠檬酸、1.0006g亚磷酸三苯酯和0.03506g叔丁基对苯二酚，用电动搅拌机混合均匀后流延成膜，再放在通风橱内12h。该薄膜的厚度为0.029mm，拉伸强度为30.74MPa。
缓释型二氧化氯抗菌膜：用AFA-II自动涂膜机在干燥后的A膜上涂布一层胶粘剂低密度聚乙烯，此时低密度聚乙烯用量为B膜质量的20％，再用涂膜机将B膜复合，制成以聚乳酸(PLA)为基材的缓释型二氧化氯抗菌膜。薄膜的厚度为0.289mm，拉伸强度为36.72MPa，二氧化氯的保留量为46.7282mg/g。在40℃，RH60％的环境下，15天后二氧化氯的保留量为6.7002ppm。在37℃下，薄膜对大肠杆菌和金色葡萄球菌的抑菌率都在85％以上。
实施例3
A膜：称量2.0031g聚乙烯醇溶于40ml浓度为45.4767ppm的稳定性二氧化氯水溶液，用电动搅拌机边倒边搅拌先溶胀，等到没有白色的团块时再加入60ml浓度为45.4767ppm的稳定性二氧化氯水溶液，再依次加入1.0334g甘油和0.1039g羧甲基纤维素钠，同样用电动搅拌机边倒边搅拌，配制成一定浓度的PVA凝胶水溶液，搅拌均匀后再经AFA-II自动涂膜机流延成膜，放在40℃、RH45％环境下24h烘干。制成薄膜的二氧化氯保留量为49.4174ppm/g，厚度为0.242mm，拉伸强度为8.23MPa。
B膜：称量4.0235g聚乳酸溶于100ml二氯甲烷，再依次加入0.1014g酒石酸、1.0106g柠檬酸三丁酯和0.0405g叔丁基对苯二酚，用电动搅拌机混合均匀后流延成膜，再放在通风橱内12h。该薄膜的厚度为0.024mm，拉伸强度为50.74MPa。
缓释型二氧化氯抗菌膜：用AFA-II自动涂膜机在干燥后的A膜上涂布一层胶粘剂乙烯-醋酸乙烯共聚物，此时乙烯-醋酸乙烯共聚物用量为B膜质量的50％，再用涂膜机将B膜复合，制成以聚乳酸(PLA)为基材的缓释型二氧化氯抗菌膜。薄膜的厚度为0.282mm，拉伸强度为53.72MPa，二氧化氯的保留量为47.1912ppm/g。在40℃，RH60％的环境下，15天后没有测出二氧化氯。在37℃下，薄膜对大肠杆菌和金色葡萄球菌的抑菌率都在70％以上。

Claims (5)

1.一种缓释型二氧化氯抗菌膜的制备工艺，其特征在于：该制备工艺是采用湿法复合将A膜和B膜复合在一起制成以聚乳酸为基材的缓释型二氧化氯抗菌膜；
所述A膜的制备工艺是：选用水凝胶聚乙烯醇作为成膜基材，用稳定性二氧化氯水溶液配制成聚乙烯醇凝胶水溶液，再经流延工艺烘干成膜；
配制聚乙烯醇凝胶水溶液时，在聚乙烯醇凝胶水溶液中添加甘油做增塑剂，添加羧甲基纤维素以增加薄膜的吸湿性，促进二氧化氯的释放，添加的甘油量为水凝胶聚乙烯醇质量的2％～52％，添加的羧甲基纤维素的质量与稳定性二氧化氯水溶液的体积比为0.1～2g:100ml；
所述B膜的制备工艺是：选用聚乳酸作为成膜基材，用二氯甲烷溶解聚乳酸，并向其中加入二氧化氯的活化剂柠檬酸或酒石酸，添加增塑剂柠檬酸三丁酯或亚磷酸三苯酯，添加抗氧化剂丁基羟基茴香醚或叔丁基对苯二酚；
A膜和B膜复合时采用低密度聚乙烯或乙烯-醋酸乙烯共聚物为粘合剂，粘合剂用量为B膜质量的10％～50％。
2.根据权利要求1所述缓释型二氧化氯抗菌膜的制备工艺，其特征在于，A膜制备工艺中，所述稳定性二氧化氯水溶液的浓度为40ppm-37000ppm，配成的聚乙烯醇凝胶水溶液中聚乙烯醇的质量浓度为1％～10％。
3.根据权利要求1或2所述缓释型二氧化氯抗菌膜的制备工艺，其特征在于，A膜制备工艺中，配制聚乙烯醇凝胶水溶液时，按配制先将40％的稳定性二氧化氯水溶液与水凝胶聚乙烯醇混合，用电动搅拌机边倒边搅拌先溶胀，等到没有白色的团块时加入余量的稳定性二氧化氯水溶液。
4.根据权利要求1所述缓释型二氧化氯抗菌膜的制备工艺，其特征在于，所述B膜的制备工艺中，活化剂的添加量为聚乳酸质量的1％～20％；增塑剂的添加量为聚乳酸质量的5％～25％；抗氧化剂的添加量为聚乳酸质量的0.1％～1％。
5.根据权利要求1所述缓释型二氧化氯抗菌膜的制备工艺，其特征在于，所述B膜的制备工艺中，用二氯甲烷溶解聚乳酸时，聚乳酸的质量与二氯甲烷的体积比为4～10g:100ml。
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