CN106012545A - 一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂 - Google Patents
一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂 Download PDFInfo
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Abstract
本发明涉及一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂，所述的油剂的组成按质量份数计，包括表面活化物10～90份，增塑剂1～50份，湿润剂1～30份，抗静电剂1～35份，抗菌剂0.5～45份，二氧化钛溶胶或氧化锌溶胶0.5～50份，粘度调和剂1～40份，分散剂0.5～50份，水10～90份。将抗菌剂与二氧化钛溶胶或氧化锌溶胶结合使用，将会产生一个高效的、多功能的环保友好型材料，由于无机纳米二氧化钛和氧化锌具有永久抗菌、抗紫外，可大幅提升材料综合性能，适量配比可降低成本。
Description
技术领域
本发明涉及用于聚酯纤维的油剂，具体涉及一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂。
背景技术
随着生产力的发展和科学技术的进步，以及对全球能源危机的预期，人类越来越重视海洋资源的开发利用。我国拥有18000多公里的海岸线和广阔的领海，随着海洋科学的飞速发展和海洋开发技术的不断提高，海洋开发事业有了突飞猛进的发展，海洋构筑物也越来越多；然而对于各种材料来说，海洋是一个十分严酷的腐蚀环境，海洋环境下材料的腐蚀尤其是海洋微生物导致的腐蚀已引起了人们广泛的关注和研究：微生物在材料表面吸附、繁殖、生长、新陈代谢等都会对材料的腐蚀破坏产生影响，导致材料的表面状态、局部微环境、材料/海水的界面特性等发生变化，从而影响腐蚀过程。
在海洋科学发展的过程中，海洋用高强纤维材料的防腐问题己成为当前急需解决的技术难题。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。
现国内外都致力于研制低毒或无毒防污材料，氟化物和有机硅化物得到了发展和应用。氟化物具有优良的耐久性、耐候性、耐化学药品性、防腐性和绝缘性；同时具有极低的非粘着性和耐污染性，但由于氟化物表层污损生物的脱落需要较高的能量，因此在低表面能防污涂料方面不如有机硅树脂系 列，同时有机氟防污涂料的研制难度比有机硅防污涂料大得多。Schmidt和我国的田军等人专门对聚四氟乙烯等有机氟树脂的防污性进行了研究，认为由于涂料为热熔成膜，其涂膜的致密性较差，因此海洋微生物很容易深入涂膜内部而粘附在涂膜的微孔内，如果涂膜的表面有CF2基团，则其防污性能更差。美国海军在氟化聚氨酯技术方面取得了很大的进展，Moniz用氟化物对聚氨酯进行了改性处理，合成了含氟量为24％(体积分数)的氟化聚氨酯，并制备了防污涂料，但其防污效果并不理想。为此，美国海军试验室的Robret等人又开发了氟含量高达31～67％的一系列氟化聚氨酯防污涂料，其表面能甚至低于纯聚四氟乙烯的表面能，但仍然没能取得满意的防污效果。
然而有机硅化物中的Si-O键的共价键能高达425KJ/mol，比一般的有机聚合物中的C-C键的共价键能(345KJ/mol)和C-O键能(351KJ/mol)大很多，加之Si-O键极性大，因此提高Si原子上连接的烷基对氧化作用的稳定性；有机硅化物受热氧化后，生成稳定的Si-O-Si键，具有优良的抗水性、耐高温性、耐化学药品性和耐候性。此外，有机硅化物还具有防水、防盐雾、防霉菌等特性，即使长期浸泡于水中，结构变化很小。James等人利用氨基硅油中的活性氢和聚氨酯中的异氰酸脂基反应，在聚氨酯侧链上引入聚硅氧烷链段，制得有机硅改性聚氨酯类防污涂料，使聚硅氧烷易于向表面迁移，从而使涂膜具有低的表面能和较好的防污性能。田军等人以有机硅改性环氧树脂为成膜物，以低表面能的聚四氟乙烯、石墨层间化合物(GIC)和氟化碳酸盐等粉末为添加剂，通过研磨制成一种防污涂料，经一年实海试验表明，只有少量的藤壶、苔藓虫、绿藻、水螅附着于涂层表面，海洋生物的覆盖面积仅为15％左右，与未涂覆该涂料的试验表面对比试样防污效果明显提高。但是，单纯的氟化物或有机硅化物都不能很好满足耐海水材料的使用。
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老化、防腐抗菌抗污油剂，在油剂配方中添加抗菌剂和二氧化钛溶胶或氧化锌溶胶，改善了聚酯纤维抗紫外老化、防腐抗污、耐水洗、抗静电等性能。
本发明所提供的技术方案为：
一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其中，所述的油剂的组成按质量份数计，包括表面活化物10～90份，增塑剂1～50份，湿润剂1～30份，抗静电剂1～35份，抗菌剂0.5～45份，二氧化钛溶胶或氧化锌溶胶0.5～50份，粘度调和剂1～40份，分散剂0.5～50份，水10～90份。
本发明将抗菌剂与二氧化钛溶胶或氧化锌溶胶结合使用，将会产生一个高效的、多功能的环保友好型材料，由于无机纳米二氧化钛和氧化锌具有永久抗菌、抗紫外，可大幅提升材料综合性能，适量配比可降低成本；此外，使用上述油剂的聚酯纤维具有优异的平滑性能、力学性能、抗静电和超疏水性能。本发明的用于聚酯纤维的耐老化、防腐抗菌抗污油剂具有防污效果好，防污期效长，经济且对环境影响小，易于工业化生产应用，也为实现无污染的海洋战略做出重大的贡献。
作为优选，所述的表面活化物为聚二甲基硅氧烷、氨基硅油或五元共聚嵌段硅油中的一种或多种。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，所述的抗菌剂为聚硅氧烷季铵盐或聚季铵盐。
进一步优选，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或聚季铵盐-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，所述的二氧化钛溶胶或氧化锌溶胶与抗菌剂的质量比 0.1:1～20:1。在油剂中添加新型硅化物提高疏水性能，并在油剂中将无机抗菌剂与有机抗菌剂复合协同增效，不仅兼具了有机系抗菌剂的即效性、持续性和无机系抗菌剂的安全性、耐热性，而且在很大程度上提高耐紫外老化，降低了抗菌剂的成本，同时改善抗菌的广谱性。
作为优选，所述的二氧化钛溶胶为纳米锐钛矿型二氧化钛溶胶或纳米金红石型二氧化钛溶胶；所述的氧化锌溶胶为纳米氧化锌溶胶。
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和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，所述的分散剂为聚乙烯醇200、聚乙烯醇400，分散剂KF60或分散剂5040。
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或聚醚型聚氨酯类增塑剂。
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，所述的油剂的组成按质量份数计，包括25～30份五元共聚嵌 段硅油，2～5份邻苯二甲酸二异壬酯，1～5份壬基酚聚氧化乙烯醚，1～5份聚季铵盐-11，1～5份二氧化钛溶胶或氧化锌溶胶，5～10份聚氧化乙烯醚，3～6份分散剂KF60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)本发明将抗菌剂与二氧化钛溶胶或氧化锌溶胶结合使用，将会产生一个高效的、多功能的环保友好型材料，由于无机纳米二氧化钛和氧化锌具有永久抗菌、抗紫外，可大幅提升材料综合性能，适量配比可降低成本。
(2)本发明在油剂中添加新型硅化物提高疏水性能，并在油剂中将无机抗菌剂与有机抗菌剂复合协同增效，不仅兼具了有机系抗菌剂的即效性、持续性和无机系抗菌剂的安全性、耐热性，而且在很大程度上提高耐紫外老化，降低了抗菌剂的成本，同时改善抗菌的广谱性。
具体实施方式
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。
氧化锌溶胶：如JC-J50C,JC-J50HW,JC-ZW,深圳晶材化工有限公司。
二氧化钛溶胶：如EFUT-GY01，EFUT-GY02，EFUT-GY03，上海依夫实业有限公司。
实施例1
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占1.9份，氧化锌溶胶占3.8份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例2
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占1.4份，氧化锌溶胶占4.3份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例3
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占3.8份，氧化锌溶胶占1.9份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例4
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，氧化锌溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例5
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占1.9份，二氧化钛溶胶占3.8份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例6
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占1.4份，二氧化钛溶胶占4.3份，蒸馏水占47.6份，聚氧化乙烯 醚占8.6份，分散剂KF60占4.7份。
实施例7
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占3.8份，二氧化钛溶胶占1.9份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例8
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例9
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：聚二甲基硅氧烷占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例10
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：氨基硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例11
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚 硅氧烷季铵盐-16占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例12
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚醚增稠剂SE占8.6份，分散剂KF60占4.7份。
实施例13
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂聚乙烯醇200溶液占4.7份。
实施例14
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂5040占4.7份。
实施例15
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，十二烷基磺酸钠占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
实施例16
用于聚酯纤维的耐老化、防腐抗菌抗污油剂的配方：五元共聚嵌段硅油 占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，乙氧基化脂肪族烷基胺占4.3份，二氧化钛溶胶占1.4份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
对比例1
用于聚酯纤维的油剂的配方：五元共聚嵌段硅油占28.6份，邻苯二甲酸二异壬酯占2.9份，壬基酚聚氧化乙烯醚占1.9份，聚季铵盐-11占5.7份，蒸馏水占47.6份，聚氧化乙烯醚占8.6份，分散剂KF60占4.7份。
对比例2
用于聚酯纤维的油剂的配方：五元共聚嵌段硅油占30.3份，邻苯二甲酸二异壬酯占3.0份，壬基酚聚氧化乙烯醚占2.0份，蒸馏水占50.5份，聚氧化乙烯醚占9.1份，分散剂KF60占5.1份。
性能实验
本发明一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂，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1～8和对比例1～2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；GB/T 9780-2005《集灰实验和耐污性实验》中提供的方法进行耐污自清洁性能测试。
分别取上述表面活化物、增塑剂、湿润剂、抗静电剂、抗菌剂、纳米二氧化钛溶胶或氧化锌溶胶、粘度调和剂、分散剂、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1-4及对比例1,2分别制备的纤维油剂对聚酯纤维的抗菌性能、耐老化、耐污级别和力学性能数据
表2为实施例5-8及对比例1,2分别制备的纤维油剂对聚酯纤维的抗菌性能、耐老化、耐污级别和力学性能数据
根据表1和表2可以看出，无机纳米二氧化钛溶胶或氧化锌溶胶对高强聚酯纤维具有优异的永久抗菌性能、优异的抗紫外性能以及优异耐热、抗静电性能；而五元共聚嵌段硅油是新助剂，在耐海水上有独特优势，同时，改善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 (10)
1.一种用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的油剂的组成按质量份数计，包括表面活化物10～90份，增塑剂1～50份，湿润剂1～30份，抗静电剂1～35份，抗菌剂0.5～45份，二氧化钛溶胶或氧化锌溶胶0.5～50份，粘度调和剂1～40份，分散剂0.5～50份，水10～90份。
2.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的表面活化物为聚二甲基硅氧烷、氨基硅油或五元共聚嵌段硅油中的一种或多种。
3.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的抗菌剂为聚硅氧烷季铵盐或聚季铵盐。
4.根据权利要求3所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，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或聚季铵盐-10、聚季铵盐-7、聚季铵盐-6、聚季铵盐-16或聚季铵盐-22。
5.根据权利要求4所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的二氧化钛溶胶或氧化锌溶胶与抗菌剂的质量比0.1:1～20:1。
6.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的二氧化钛溶胶为纳米锐钛矿型二氧化钛溶胶或纳米金红石型二氧化钛溶胶；所述的氧化锌溶胶为纳米氧化锌溶胶。
7.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的增塑剂为邻苯二甲酸酯或聚酯增塑剂。
8.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的分散剂为聚乙烯醇200、聚乙烯醇400，分散剂KF60或分散剂5040。
9.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，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。
10.根据权利要求1所述的用于聚酯纤维的耐老化、防腐抗菌抗污油剂，其特征在于，所述的油剂的组成按质量份数计，包括25～30份五元共聚嵌段硅油，2～5份邻苯二甲酸二异壬酯，1～5份壬基酚聚氧化乙烯醚，1～5份聚季铵盐-11，1～5份二氧化钛溶胶或氧化锌溶胶，5～10份聚氧化乙烯醚，3～6份分散剂KF60和40～60份蒸馏水。
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