CN105908512B - 一种用于聚酯纤维的耐海水抗菌油剂 - Google Patents
一种用于聚酯纤维的耐海水抗菌油剂 Download PDFInfo
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Abstract
本发明涉及一种用于聚酯纤维的耐海水抗菌油剂，所述的耐海水抗菌油剂的组成按质量份数计，包括表面活化物10～80份，增塑剂1～25份，湿润剂1～18份，抗静电剂1～35份，防腐剂0.5～22份，粘度调和剂2～31份，水10～90份。该耐海水抗菌油剂组分中添加防腐剂和表面活化物，使得耐海水抗菌油剂能够改善聚酯纤维，使其具有优异的平滑耐磨性能、超疏水性和防污性，而且具有优异的抗静电和抗菌性能。
Description
技术领域
本发明涉及耐海水抗菌油剂，具体涉及一种用于聚酯纤维的耐海水抗菌油剂。
背景技术
近年来，高强聚酯纤维材料在海洋中的应用越来越广，主要运用于海洋石油平台的固定绳索、舰船缆绳、鱼网、船帆、防护衣、皮划艇等。然而海洋环境是一个复杂的环境，其中盐度、海水温度、海洋污染物、海洋生物、溶氧量等都会影响聚酯纤维材料性能和和使用寿命，并制约其在海洋中的应用，如果没有高强度、强耐腐蚀性、无毒或低毒性的高性能材料作为保证，发展海洋科技产业将受到很大限制。因此，加强对纤维材料的耐海水腐蚀性能研究有着重要的意义。
化纤油剂是在化学纤维的纺丝、拉伸及后处理的过程中，为了减少丝束与导丝构件摩擦，消除在熔融纺丝过程中产生的静电，在纺丝、纺织前喷附在纤维表面上的化学助剂。
为了降低海水腐蚀、防止海洋附着生物的附着、减少耐海水抗菌层的起泡和脱落现象，研究者开始利用抗菌剂和活化物协同处理材料，如使用含氟活化物与金属抗菌剂含银、铜、锡类协同可获得优异的防腐抗菌效果。金属离子抗菌剂对各种病毒、细菌具有广谱，灭菌率高、安全性好、长效、不产生耐药性等特点，可以有效地杀死或抑制细菌的生长。但是有机抗菌剂耐热稳定性差，易挥发或水解，分解产物和挥发性组分容易对人类的皮肤和眼睛等造成刺激，故使用安全性差，寿命短。因此在纤维、木材、涂料、塑料(特别是工程塑料)加工成型等高温、高压、高剪切的加工条件下，有机抗菌剂的使用受到限制。例如汤庆国等发表了金属离子抗菌剂的抗菌效果及应用(研究环境与健康杂志.2005年3月第22卷第2期)，具体公开了将过渡族金属离子、氧化物光触媒或有机抗菌组分担载到无机矿物上形成性能优异的新型抗菌材料，在改善人类的生活环境，提高人们健康水平方面将发挥越来越重要的作用。但是，金属抗菌剂易于析出，导致材料抗菌效果差，且对海洋产生金属污染。二十世纪八十年代初期，全世界防污涂料中所用抗菌剂为有机锡，有机锡高聚物不断发生水解和溶解，从而不断释放出有机锡毒料，达到长期防污的目的。但它对海水中的一些生物具有毒性，并引起生物发生变异，导致畸形，更为严重的是由于有机锡很稳定，经过很长时间也不易分解，它们经过海洋贝类和鱼类的渠道进入人类的食物链，直接危害人体的健康。因此近年来各沿海国家纷纷立法限制有机锡的使用。
目前，由于对含有机锡抗菌剂的限制越来越严格，无锡抗菌剂的市场潜力也越来越大。世界上很多国家正在加快开发研制不含锡的抗菌剂。但是值得指出的是，以氧化亚铜类加入辅助毒剂(如氧化吡啶硫酚的锌、铜络合物等)为抗菌剂，海洋中或海港中铜元素的大量积累，会导致海藻的大量死亡。且有研究表明，铜加上辅助毒剂对海洋生物的危害几乎等同于有机锡，因此，该类抗菌剂最终也将被禁用。银离子抗菌性能较强，且对细菌不易产生抗药性突变，安全性好。研究表明，银离子抗菌剂急性毒性(LD50)大于2000mg/kg，皮肤一次刺激呈无刺激性反应，基因突变呈阴性。但材料中银离子不够稳定，在紫外线照射下银离子易还原为金属银，银氧化后制品变黑，变灰，抗菌性能下降。
为避免金属类抗菌剂的缺陷，降低抗菌剂的价格，保证其抗菌广谱性，因此研发出聚酯纤维用绿色环保永久型的耐海水抗菌油剂逐步成为当前研究的热点，也是未来海洋领域的发展方向。
发明内容
本发明的目的在于针对现有技术的不足，提供一种用于聚酯纤维的耐海水抗菌油剂，在油剂组分中添加防腐剂和表面活化物，改善了材料的防腐抗菌、耐久性、超疏水和抗静电等性能。
为解决上述技术问题，本发明所提供的技术方案为：
一种用于聚酯纤维的耐海水抗菌油剂，所述的耐海水抗菌油剂的组成按质量份数计，包括表面活化物10～80份，增塑剂1～25份，湿润剂1～18份，抗静电剂1～35份，防腐剂0.5～22份，粘度调和剂2～31份，水10～90份。
上述技术方案中，油剂组分中添加防腐剂和表面活化物，使得耐海水抗菌油剂能够改善聚酯纤维，使其具有优异的平滑耐磨性能、超疏水和防污性，而且具有优异的抗静电和抗菌性能。
作为优选，所述的表面活化物为聚二甲基硅氧烷、聚硅氧烷季铵盐、氨基硅油或五元共聚嵌段硅油中的一种或多种。所述的聚硅氧烷季铵盐为聚硅氧烷季铵盐-16；所述的氨基硅油为氨乙基氨丙基聚二甲基硅氧烷或氨基封端聚二甲基硅氧烷。
作为优选，所述的防腐剂为聚硅氧烷季铵盐和聚季铵盐的复配物。由于海洋中存在大量的藻类和细菌，环境复杂，为了避免海洋生物和细菌的附着，该技术方案中采用聚硅氧烷季铵盐和聚季铵盐的复配物。虽然单一的聚季铵盐也具有避免海洋生物和细菌的附着的作用，但是单一的聚季铵盐容易在水中溶出，导致抗菌性大幅度降低的缺陷，而聚硅氧烷季铵盐和聚季铵盐的复配物能够避免该类缺陷，耐水洗性能较好，具有永久性。
进一步优选，所述的聚硅氧烷季铵盐与聚季铵盐的质量配比为1/1～20/1。
作为优选，所述的聚硅氧烷季铵盐为聚硅氧烷季铵盐-16；所述的聚季铵盐为聚季铵盐-11、聚季铵盐-10、聚季铵盐-7、聚季铵盐-6、聚季铵盐-16或聚季铵盐-22。
作为优选，所述的粘度调和剂为聚醚类增稠剂、丙烯酸类增稠剂或羟乙基纤维素增稠剂中的一种或多种。进一步优选，所述的聚醚类增稠剂为聚氧化乙烯醚、聚醚增稠剂SE、非离子聚醚型聚氨酯类增塑剂、聚醚型聚氨酯类增塑剂。
作为优选，所述的增塑剂为邻苯二甲酸酯或聚酯增塑剂。进一步优选，所述的邻苯二甲酸酯为邻苯二甲酸二辛酯或邻苯二甲酸二异壬酯。
作为优选，所述的湿润剂为阴离子型表面活性剂或非离子型表面活性剂。所述的阴离子型表面活性剂为烷基硫酸盐、磺酸盐、脂肪酸、脂肪酸酯硫酸盐、羧酸皂类或磷酸酯等。所述的非离子型表面活性剂为聚氧乙烯烷基酚醚、聚氧乙烯脂肪醇醚、聚氧乙烯聚氧丙烯嵌段共聚物、硅醇等。进一步优选，所述的湿润剂为壬基酚聚氧化乙烯醚(P-40)。
作为优选，所述抗静电剂为阳离子抗静电剂、阴离子抗静电剂或非离子型抗静电剂。进一步优选，所述的阳离子抗静电剂为长链的烷基季铵(如聚季铵盐-11)、磷盐类，阴离子抗静电剂为烷基磺酸或磷酸等，非离子型抗静电剂为乙氧基化脂肪族烷基胺类等。
作为优选，所述的耐海水抗菌油剂的组成按质量份数计，包括12～18份五元共聚嵌段硅油，1～5份邻苯二甲酸二异壬酯，1～5份壬基酚聚氧化乙烯醚，1～15份聚季铵盐-11，10～20份聚硅氧烷季铵盐-16，5～13份聚氧化乙烯醚和40～60份蒸馏水。
同现有技术相比，本发明的有益效果体现在：
(1)本发明在耐海水抗菌油剂中添加表面活化物来增加疏水性，并在纤维油剂中添加多种辅助剂后使聚酯纤维的防腐抗菌、超疏水性、抗静电性能得到提升，同时提高抗菌的持久性，并通过复配，减少原料的使用，从而降低生产成本。
(2)本发明耐海水抗菌油剂中通过选取合适的防腐剂，对聚硅氧烷季铵盐和聚季铵盐进行复配，提高了抗菌性能的持久性，降低了成本。
具体实施方式
下面通过实施例对本发明进行具体的描述。
五元共聚嵌段硅油：如BF-100,BF-440,BF-660,东阳市兴邦化学有限公司。
氨基硅油：如BF-2100,BF-2150,BF-9120,东阳市兴邦化学有限公司。
实施例1
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为五元共聚嵌段硅油占15份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占1份，聚硅氧烷季铵盐-16占20份，蒸馏水占50份，聚氧化乙烯醚占9份。
实施例2
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为五元共聚嵌段硅油占15份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占6份，聚硅氧烷季铵盐-16占15份，蒸馏水占50份，聚氧化乙烯醚占9份。
实施例3
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为五元共聚嵌段硅油占15份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占11份，聚硅氧烷季铵盐-16占10份，蒸馏水占50份，聚氧化乙烯醚占9份。
实施例4
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为聚二甲基硅氧烷占15份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占11份，聚硅氧烷季铵盐-16占10份，蒸馏水占50份，聚氧化乙烯醚占9份。
实施例5
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为氨基硅油占15份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占11份，聚硅氧烷季铵盐-16占10份，蒸馏水占50份，聚氧化乙烯醚占9份。
实施例6
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为聚硅氧烷季铵盐占25份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占11份，蒸馏水占50份，聚氧化乙烯醚占9份。
对比例1
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为五元共聚嵌段硅油占30份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，聚季铵盐-11占6份，蒸馏水占50份，聚氧化乙烯醚占9份。
对比例2
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为五元共聚嵌段硅油占30份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，蒸馏水占50份，聚氧化乙烯醚占9份。
对比例3
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为聚二甲基硅氧烷占30份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，蒸馏水占50份，聚氧化乙烯醚占9份。
对比例4
用于聚酯纤维的耐海水抗菌油剂的配方：各成分的重量配比范围为氨基硅油占30份，邻苯二甲酸二异壬酯占3份，壬基酚聚氧化乙烯醚占2份，蒸馏水占50份，聚氧化乙烯醚占9份。
性能实验
本发明一种用于聚酯纤维的耐海水抗菌油剂，由于不同的配比其性能出现不同程度差别。因此，采用实施例1～6和对比例1～4的配方，将其应用于聚酯纤维(PET)材料中。
参照：GB/T 14337-2008《化学纤维短纤维拉伸性能试验方法》中提供的方法进行力学性能测试；GB/T 20944.3-2008《纺织品抗菌性能的评价第3部分：振荡法》提供的方法进行抗菌性能测试。分别取上述活化物、增塑剂、润湿剂、抗静电剂、防腐剂、粘度调和剂、蒸馏水以不同比例混合均匀后，将高强聚酯纤维浸渍在油剂中，干燥完成后，进一步测试抗菌性能和力学性能，部分试验结果如表1、表2所示：
表1为实施例1-6及对比例1-4分别制备的耐海水抗菌油剂对聚酯纤维的抗菌性能数据
表2为实施例1-3及对比例1,2分别制备的耐海水抗菌油剂对聚酯纤维的力学性能数据
根据表1和表2可以看出，实施例1～3的配方中，聚硅氧烷季铵盐类对高强聚酯纤维具有优异的抗菌性能和优异的耐水洗性能以及优异的超疏水性能，聚硅氧烷季铵盐-16化合物是新助剂，在耐海水上有独特优势，同时，增加耐海水聚酯纤维的成膜稳定性，并提高力学性能，从而延长寿命，拓宽应用范围。
Claims (5)
1.一种用于聚酯纤维的耐海水抗菌油剂，其特征在于，所述的耐海水抗菌油剂的组成按质量份数计，包括表面活化物10～80份，增塑剂1～25份，湿润剂1～18份，抗静电剂1～35份，防腐剂0.5～22份，粘度调和剂2～31份，水10～90份；
所述的表面活化物为聚二甲基硅氧烷、聚硅氧烷季铵盐、氨基硅油或五元共聚嵌段硅油中的一种或多种；
所述的防腐剂为聚硅氧烷季铵盐和聚季铵盐的复配物；所述的聚硅氧烷季铵盐与聚季铵盐的质量配比为1/1～20/1；所述的聚硅氧烷季铵盐为聚硅氧烷季铵盐-16；所述的聚季铵盐为聚季铵盐-11、聚季铵盐-10、聚季铵盐-7、聚季铵盐-6、聚季铵盐-16或聚季铵盐-22。
2.根据权利要求1所述的用于聚酯纤维的耐海水抗菌油剂，其特征在于，所述的粘度调和剂为聚醚类增稠剂、丙烯酸类增稠剂或羟乙基纤维素增稠剂中的一种或多种。
3.根据权利要求1所述的用于聚酯纤维的耐海水抗菌油剂，其特征在于，所述的增塑剂为邻苯二甲酸酯或聚酯增塑剂。
4.根据权利要求1所述的用于聚酯纤维的耐海水抗菌油剂，其特征在于，所述的湿润剂为阴离子型表面活性剂或非离子型表面活性剂。
5.根据权利要求1所述的用于聚酯纤维的耐海水抗菌油剂，其特征在于，所述的耐海水抗菌油剂的组成按质量份数计，包括12～18份五元共聚嵌段硅油，1～5份邻苯二甲酸二异壬酯，1～5份壬基酚聚氧化乙烯醚，1～15份聚季铵盐-11，10～20份聚硅氧烷季铵盐-16，5～13份聚氧化乙烯醚和40～60份蒸馏水。
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Application publication date: 20160831 Assignee: ZHEJIANG UNIFULL INDUSTRIAL FIBRE Co.,Ltd. Assignor: ZHEJIANG SCI-TECH University Contract record no.: X2024980016645 Denomination of invention: A seawater resistant and antibacterial oil agent for polyester fibers Granted publication date: 20180619 License type: Common License Record date: 20240929 |