CN103290679B - 一种含有三唑环的纺织品抗菌整理剂 - Google Patents
一种含有三唑环的纺织品抗菌整理剂 Download PDFInfo
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Abstract
本发明公开了一种含有三唑环的纺织品抗菌整理剂的制备与应用，以三唑衍生物为主抗菌基团，三嗪衍生物中的三氮苯环为辅助抗菌基团，三嗪衍生物的活性取代基为潜在的反应基团，在0-40℃和催化剂作用下一步法完成反应，制备反应型三唑抗菌整理剂。该抗菌剂配置8-20％的抗菌剂乳液用于棉织物抗菌整理，棉织物在40-80℃保温反应40min，随后加入碳酸钠，继续反应40min，取出织物水洗晾干即可完成整理过程。经过抗菌整理后的棉织物对大肠杆菌和金黄色葡萄球菌具有良好的抑菌作用，并且具有较高的耐洗性能。
Description
技术领域
本发明属于抗菌整理剂的领域，特别是涉及一种含有三唑衍生物抗菌整理剂的制备与应用方法。
背景技术
由于人体出汗，皮脂和表面落屑等引起微生物的迅速繁殖，特别是在潮湿、营养和合适的温度下。微生物的繁殖在织物上会生成菌斑，使纺织品产生霉变、脆化甚至变质，同时，微生物分解各种有机物，产生不愉快的气味，甚至会使纺织品变色，以致纺织品应用过程中对人体产生不良影响。纺织品抗菌整理的目的是赋予纺织品良好的抗菌功能，保护纺织品不被霉菌等降解，并防止微生物传播，降低公共环境的交叉感染率；同时，还可阻止细菌在织物上不断繁殖而产生的臭气，改善服用环境。因此研究纺织品的抗菌整理意义重大。
抗菌整理织物可广泛用于人们的内衣、睡衣、运动衣、袜子、鞋衬布、婴儿尿布、床单、被套、毛毯、餐巾、毛巾、沙发布、窗帘布、地毯等。2001-2005年，西欧抗菌纺织品产量估计年均增长高达15％，是纺织品市场中增长最快的领域。该类产品85％为运动服、袜子、鞋垫和女式内衣。与抗菌服装相比，抗菌纤维的市场更加广阔，因此抗菌整理已经成为国内外的研究热点。
理想的纺织品抗菌整理应满足以下几个条件：第一，对细菌和真菌具有广谱抗菌性，同时对消费者低毒或无毒，不会引起致毒、过敏或刺激性。第二，整理效果应具有耐久性，耐机洗、干洗和热压烫，这是抗菌整理面临的最大挑战。第三，整理过程不会对纺织品的品质或外观带来不利影响。最后，抗菌整理最好能与纺织化学加工(如染色工艺)相容，不产生对加工者和环境有害的物质。
纺织品抗菌性能的高低取决于所用抗菌整理剂性能的优劣。纺织品用抗菌剂按照结构的不同，可分为有机类、无机类和天然生物抗菌剂3大类型。无机类抗菌剂主要是贵重金属离子及金属氧化物纳米粒子。这些整理剂均属于小分子物质，只能通过浸轧、喷涂等方式用于纺织品，这类抗菌剂使用时会影响纺织品的色泽和稳定性，在纺织长期使用过程中，抗菌剂会逐渐流失而减弱抗菌效果。有机类抗菌剂主要包括季铵盐、聚六亚甲基双胍、氯代酚、卤胺化合物、壳聚糖、甜菜碱等，这些抗菌剂具有见效快、杀菌能力强的特点，但使用时却易溶出，不耐阴离子洗涤剂洗涤，高温条件下易产生二噁英类致癌物质，并且碱性条件下易失去抗菌性或释放刺激皮肤的游离氯等。天然生物抗菌剂来源于生物体，主要包括多糖、多肽及糖肽聚合物类物质等。天然抗菌剂以壳聚糖应用最多，在应用过程中会影响织物手感、耐久性、耐热性，因此限制了其大规模应用。上述抗菌剂根据溶出性能不同，又可分为溶出性和非溶出性两大类。溶出性抗菌剂是靠缓慢释放到环境中的抗菌剂起杀菌或抑菌作用，对环境有一定的影响，抗菌效果也会随着洗涤次数增加而不断减弱。而非溶出性抗菌剂一般为化学键合 在纺织品上的抗菌剂，不会因为洗涤而流失，具有持久的抗菌活性。
三唑环是一种由三个氮原子和两个碳原子组成的五元杂环，是一类具有广泛生物活性的杂环化合物，对常见真菌病害有很好的防治效果，成为发展最迅速的一类抗菌剂。近几十年来以三唑酮、三唑醇为代表的三唑类抗菌剂，以其高效、低毒和广谱杀菌等优点而备受研究者的重视。在医药领域，三唑环作为药效团呈现出多种生物活性，已有众多的三唑衍生物作为抗真菌、抗病毒、抗肿瘤、抗惊厥等药物广泛应用于临床。三唑类化合物还对多种疾病有着良好的药效，例如催眠、止痛、抗结核、抗过敏和抗抑郁等方面。三唑类化合物在农业上用作杀菌剂，同时还具有除虫、除螨、除草和植物生长调节等功能，已成为新农药开发的重要领域。
三唑类化合物的杀菌作用来自于三唑环，三唑环具有优良的化学反应性能，出色的生物活性和良好的金属离子配位的能力。三氮唑化合物的抗真菌作用机理是抑制真菌细胞膜中麦角甾醇的生物合成，从而抑制真菌细胞的生长，最终导致真菌细胞的死亡。麦角甾醇是真菌细胞膜的重要组成部分，对真菌细胞正常的生长繁殖起重要作用。在真菌麦角甾醇生物合成途径中，要经过一系列酶促反应。其中24-亚甲基双氢羊毛甾醇的14C上的α位去甲基化反应是麦角甾醇合成的关键一步，在反应过程中需要由氧原子与血红素卟啉和单氧化酶复合物上的亚铁原子配位结合，形成的铁氧配合物作为催化剂。三氮唑类杀菌剂进入到菌体内部后，其4位N元素与菌中的铁卟啉的中心铁进行配位，其结果是阻碍了铁卟啉铁氧络合物的形成，如式1所示。14C上的α位去甲基化反应中断，造成真菌细胞中羊毛甾醇蓄积，麦角甾醇的生物合成受阻，改变了真菌细胞膜的化学组成，导致膜通透性以及连接于膜上的许多酶活性发生相应的改变，从而达到抑制真菌生长的作用。
三唑类杀菌剂为有机小分子抗菌剂，属于溶出型抗菌剂，虽然具有优良的抗菌性能，但在织物上应用时，存在容易被洗涤掉的缺点，并且对纤维素纤维的亲和力较差， 在纺织品上应用较少。针对上述三唑类杀菌剂的高效、低毒和广谱的优点，通过化学键合将其引入抗菌剂中，并就将其应用于纺织品的抗菌整理。
发明内容
本发明针对三唑类杀菌剂在棉织物上应用的易洗性和缺乏亲和力的缺点，提供一种含有反应性基团的三唑类的制备与应用方法，通过化学反应将三唑类键合到棉织物上，提高抗菌整理的耐洗性和耐久性。
本发明的反应型三唑抗菌剂以三唑醇类衍生物为主抗菌基团，三嗪衍生物中的三氮苯环为辅助抗菌基团，三嗪衍生物的活性取代基为潜在的反应基团，制备的反应型三唑醇杀菌剂结构式如2所示：
式中R3或R4为Cl，Br，F，NH2，NHCH3，NHCOCH3或R5为 其中X为卤素，烷基或芳基。
上述抗菌剂中主要依靠三唑化合物对各种菌类产生抑制作用。与菌体接触时，三唑化合物能够迅速的进入到菌体内部，阻碍了铁卟啉铁氧络合物的形成，抑制底物脱甲基化反应，导致真菌细胞膜受损，达到抑菌和杀菌功效。由式(1)可以看出三唑抗菌剂的药效基团为三唑环，因此环上的R2位取代基的改变基本不会影响化合物的抗菌活性，因此选择在R2位上引入潜在反应基团。
上述抗菌剂中以卤代均三嗪衍生物为潜在反应基团，卤代均三嗪衍生物分子结构中含有一个稳定的六元三氮苯环和三个活泼的氯原子。三氮苯也是常见抗菌剂的重要中间体，三氮苯环具有芳香性和丰富的电子，这就决定了它具有易于接受质子和络合金属离子的性质，三氮苯环通过一些非共价键力如氢键、配位键、离子-偶极、范德华力、疏水效应及π-π堆积形成超分子聚体，使之具有抗真菌、抗细菌等功能。三氮苯环与异噻唑啉酮两部分均有抗菌作用，且相互促进，强化抗菌活性。此外，卤代均三嗪中的三个活性卤原子可以与-OH，-NH2等含有活泼氢的基团取代，形成不同的含有均三嗪结构的反应型抗菌剂。因此，卤代均三嗪在反应性抗菌剂中起到双重作用，既可以作为反应基团，又能够提高抗菌剂的抗菌活性。
实施该发明的技术方案包括两部分，第一部分是反应型三唑杀菌剂的合成。在装有电动搅拌器、温度计的四口烧瓶中，加入适量的三唑醇、催化剂和溶剂，搅拌下溶解，降温至0-40℃，滴加三聚氯氰溶液，滴加结束后，再于0-40℃下反应5-12h，冷却至室温过滤，将反应液减压蒸馏，得到粘稠液体，蒸馏水重结晶，得白色固体，即为反应型三唑杀菌剂。
第二部分是棉织物的抗菌整理，将第一步中所得抗菌剂在非离子表面活性剂的乳化作用形成乳液，其中含有8-20％的抗菌剂。按照浴比为1∶15进行浸渍处理，整理过程如下，将织物在常温下进入工作液中，浸泡5min，升温至40-80℃，加入20g/L的氯化钠，保温反应40min，加入15g/L碳酸钠，继续反应40min，取出织物，水洗2次，在空气中自然晾干即可。
上述抗菌剂能够通过三氮苯环上的活性氯原子与棉纤维反应，使三唑杀菌剂键合到棉织物上，从而使织物上的抗菌剂具有良好的耐洗性，从根本解决了抗菌整理的耐久性问题。
上述抗菌整理后白色织物的白度略有降低，整理过程不影响织物的顶破强度等物理机械性能。
上述抗菌整理后织物对革兰氏阳性菌---金黄色葡萄球菌和革兰氏阴性菌---大肠杆菌具有良好的抑菌效果。
下面结合实例对本发明内容进行描述。
具体实施方式
实施例1
在装有电动搅拌器和温度计的500mL的四口烧瓶中，加入14.5g三唑醇，少量催化剂和150mL氯仿，搅拌溶解，降温至0-5℃，滴加100mL三聚氯氰的氯仿溶液(其中含有三聚氯氰11.5g)，滴加结束后，再于0-5℃下反应12h，室温下过滤，去除催化剂，将反应液减压蒸馏，得到粘稠液体，蒸馏水重结晶，得白色固体，即为反应型三唑杀菌剂。产品收率62.3％。
将第一步中所得抗菌剂适量，壬基酚聚氧乙烯醚5g、聚氧乙烯醚失水山梨醇酯4.6g加入到100g去离子水中，配置乳化工作液。按照浴比为1∶15对纯棉白色针织织物进行浸渍处理。将织物在常温下进入工作液中，浸泡5min，升温至40℃，加入20g/L的氯化钠，保温反应40min，加入15g/L碳酸钠，继续反应40min，取出织物，水洗2次，在空气中自然晾干即可。
用大肠杆菌ATCC8099和金黄色葡萄球菌ATCC6538对经过抗菌整理的织物进行抑菌实验。按照GB/T20944.3-2008振荡法进行抗菌性测试。按照GB/T19976-2005纺织品顶破强力钢球法和GB8425-1987纺织品白度仪器评定方法对织物的强度和颜色改变进行评价。按照日本JISL-0217中103方法对织物的耐洗性能进行测定，使用的洗涤剂按GB/T8629附录B规定执行。上述测试结果如表1-3所示。
表1抗菌剂浓度对抗菌率影响
表2抗菌整理对织物顶破强度和白度影响
| 抗菌液用量％ | 白度 | 顶破强力N |
| 0 | 98.7 | 424.3 |
| 5 | 97.4 | 424.1 |
| 10 | 97.2 | 423.7 |
| 15 | 96.4 | 423.2 |
| 20 | 95.2 | 423.5 |
表3水洗次数对抗菌率的影响
注：抗菌剂浓度为10％
实施例2
在装有电动搅拌器和温度计的500mL的四口烧瓶中，加入14.5g三唑醇，少量催化剂和150mL氯仿，搅拌加热溶解，升温至温至40℃，滴加55g/L的1-氨基3，5二氯均三嗪的氯仿溶液180mL，滴加结束后，滴加结束后，再于40℃反应12h，冷却至室温下过滤，去除催化剂，将反应液减压蒸馏，得到粘稠液体，蒸馏水重结晶，得到白色固体，即为反应型三唑杀菌剂。产品收率54.1％。
将第一步中所得抗菌剂10g，壬基酚聚氧乙烯醚3.5g、聚氧乙烯醚失水山梨醇酯3.5g加入到83g去离子水中，配置乳化工作液。按照浴比为1∶15对纯棉白色针织织物进行浸渍处理。将织物在常温下进入工作液中，浸泡5min，升温至70℃，加入20g/L的氯化钠，保温反应40min，加入15g/L碳酸钠，继续反应40min，取出织物，水洗2次，在空气中自然晾干即可。
将所得织物进行抑菌性和物理机械性能测试，测试结果如表4-6所示。
表4抗菌剂浓度对抗菌率影响
表5抗菌整理对织物顶破强度和白度影响
| 抗菌液用量％ | 白度 | 顶破强力N |
| 0 | 98.7 | 424.3 |
| 5 | 94.4 | 423.4 |
| 10 | 93.9 | 423.5 |
| 15 | 93.9 | 424.2 |
| 20 | 93.2 | 422.9 |
表6水洗次数对抗菌率影响
注：抗菌剂浓度为10％
Claims (1)
1.一种含有三唑环的纺织品抗菌整理剂，其特征在于以三唑衍生物为主抗菌基团，三嗪衍生物中的三氮苯环为辅助抗菌基团，三嗪衍生物的活性取代基为潜在的反应基团，抗菌剂具有式1所示结构，
式中R1为或其中X为卤素，烷基或芳基，R2或R3为Cl，Br，F，NH2，NHCH3，NHCOCH3或
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945033A (en) * | 1957-05-29 | 1960-07-12 | Geigy Ag J R | 7-triazinylamino-3-phenyl coumarins |
| US4988811A (en) * | 1984-07-20 | 1991-01-29 | Minnesota Mining And Manufacturing Company | 5-(1,2,4)-triazolyl-S-triazines |
| US5118596A (en) * | 1989-03-08 | 1992-06-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| CN1632216A (zh) * | 2004-11-03 | 2005-06-29 | 华南理工大学 | 多功能棉织物整理剂及其制备方法 |
| WO2007083840A1 (en) * | 2006-01-19 | 2007-07-26 | Fujifilm Corporation | Ink, inkjet ink, inkjet recording method and method for improving weather resistance of color image material |
| CN101659660A (zh) * | 2008-08-28 | 2010-03-03 | 中国药科大学 | 取代苯基偶联的1,3,4-噻(噁)二唑衍生物制备,及其作为除草剂 |
| CN101686688A (zh) * | 2007-04-03 | 2010-03-31 | 杜邦公司 | 取代苯杀真菌剂 |
| CN102573483A (zh) * | 2009-06-08 | 2012-07-11 | 加利福尼亚资本权益有限责任公司 | 三嗪衍生物及其治疗应用 |
| WO2013047411A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 新規なトリアジン誘導体、紫外線吸収剤 |
-
2013
- 2013-04-13 CN CN201310172683.4A patent/CN103290679B/zh not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2945033A (en) * | 1957-05-29 | 1960-07-12 | Geigy Ag J R | 7-triazinylamino-3-phenyl coumarins |
| US4988811A (en) * | 1984-07-20 | 1991-01-29 | Minnesota Mining And Manufacturing Company | 5-(1,2,4)-triazolyl-S-triazines |
| US5118596A (en) * | 1989-03-08 | 1992-06-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| CN1632216A (zh) * | 2004-11-03 | 2005-06-29 | 华南理工大学 | 多功能棉织物整理剂及其制备方法 |
| WO2007083840A1 (en) * | 2006-01-19 | 2007-07-26 | Fujifilm Corporation | Ink, inkjet ink, inkjet recording method and method for improving weather resistance of color image material |
| CN101686688A (zh) * | 2007-04-03 | 2010-03-31 | 杜邦公司 | 取代苯杀真菌剂 |
| CN101659660A (zh) * | 2008-08-28 | 2010-03-03 | 中国药科大学 | 取代苯基偶联的1,3,4-噻(噁)二唑衍生物制备,及其作为除草剂 |
| CN102573483A (zh) * | 2009-06-08 | 2012-07-11 | 加利福尼亚资本权益有限责任公司 | 三嗪衍生物及其治疗应用 |
| WO2013047411A1 (ja) * | 2011-09-29 | 2013-04-04 | 富士フイルム株式会社 | 新規なトリアジン誘導体、紫外線吸収剤 |
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