CN103290678B - 一种用于纺织品抗菌整理剂 - Google Patents
一种用于纺织品抗菌整理剂 Download PDFInfo
- Publication number
- CN103290678B CN103290678B CN201310172543.7A CN201310172543A CN103290678B CN 103290678 B CN103290678 B CN 103290678B CN 201310172543 A CN201310172543 A CN 201310172543A CN 103290678 B CN103290678 B CN 103290678B
- Authority
- CN
- China
- Prior art keywords
- bacterial
- agent
- finishing
- textiles
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 239000004753 textile Substances 0.000 title claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000002421 anti-septic effect Effects 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 150000003921 pyrrolotriazines Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229920000742 Cotton Polymers 0.000 abstract description 10
- -1 tri-nitrogen benzene rings Chemical group 0.000 abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 4
- 241000588724 Escherichia coli Species 0.000 abstract description 3
- 125000001424 substituent group Chemical group 0.000 abstract description 3
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical compound C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 abstract 2
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 abstract 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 238000007730 finishing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000003115 biocidal effect Effects 0.000 description 21
- 230000008569 process Effects 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 239000003899 bactericide agent Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 6
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000004599 antimicrobial Substances 0.000 description 6
- 230000009172 bursting Effects 0.000 description 6
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 239000012224 working solution Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 241000233866 Fungi Species 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940064004 antiseptic throat preparations Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- DQJCDTNMLBYVAY-ZXXIYAEKSA-N (2S,5R,10R,13R)-16-{[(2R,3S,4R,5R)-3-{[(2S,3R,4R,5S,6R)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-5-(ethylamino)-6-hydroxy-2-(hydroxymethyl)oxan-4-yl]oxy}-5-(4-aminobutyl)-10-carbamoyl-2,13-dimethyl-4,7,12,15-tetraoxo-3,6,11,14-tetraazaheptadecan-1-oic acid Chemical compound NCCCC[C@H](C(=O)N[C@@H](C)C(O)=O)NC(=O)CC[C@H](C(N)=O)NC(=O)[C@@H](C)NC(=O)C(C)O[C@@H]1[C@@H](NCC)C(O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DQJCDTNMLBYVAY-ZXXIYAEKSA-N 0.000 description 1
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical class ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 102000002068 Glycopeptides Human genes 0.000 description 1
- 108010015899 Glycopeptides Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910003204 NH2 Inorganic materials 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 229920002413 Polyhexanide Polymers 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
本发明公开了一种用于纺织品抗菌整理剂的制备与应用，以苯并异噻唑啉酮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苯并异噻唑啉酮抗菌整理剂。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。本发明制备抗菌剂的方法简单，原料来源充足，适于工业化推广。
Description
技术领域
本发明属于抗菌整理剂的领域，特别是涉及一种反应型苯并异噻唑啉酮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(大部分是细菌类，也有霉菌和酵母菌等真菌)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，以致在穿着或应用过程中人体不适或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。
满足上述条件的抗菌整理过程中，抗菌剂成为研究的重点，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，这类杀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。
异噻唑啉酮类化合物是杂环化合物的一种，是新型的广谱、高效、低毒的杀菌抗 菌剂，其对多种细菌和真菌具有杀菌活性，如格兰氏阳性细菌、格兰氏阴性细菌、异氧菌、真菌、酵母菌和藻类等具有较好的抑制效果。大约0.5-1ppm的活性浓度下便可广泛地抑制各类型微生物的生长。该物质废弃后，在环境中能够快速降解，降解后在环境中快速隔离，不形成生物积累。因此，广泛应用于工业循环冷却水、粘合剂、纺织、涂料、造纸、建材、制革、轻工、金属加工油、农林环保等领域。异噻唑啉酮类是目前性能价格比最具优势的杀菌抗菌剂之一。
异噻唑啉酮类杀菌剂为有机小分子抗菌剂，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，并且异噻唑啉酮类杀菌剂对纤维素纤维的亲和力较差，在纺织品上应用较少。
发明内容
本发明针对异噻唑啉酮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苯并异噻唑啉酮杀菌剂的制备与应用方法，通过化学反应将苯并异噻唑啉酮键合到棉织物上，提高抗菌整理的耐久性，该方法工艺简单，产品收率较高。
本发明的反应型苯并异噻唑啉酮抗菌剂以苯并异噻唑啉酮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，制备的反应型苯并异噻唑啉酮杀菌剂结构式如1所示：
式中R1或R2为Cl，Br，F，NH2，NHCH3，NHCOCH3或R3或R4为H，CH3，CH2CH3，CH2CH2CH2CH3，Cl或Br。
上述抗菌剂中主要依靠异噻唑啉酮类化合物对各种菌类产生抑制作用。与菌体接触时，异噻唑啉酮类化合物能够迅速的进入到菌体内部，异噻唑啉酮类化合物中的S原子和N原子是与菌体作用的主要位置，能够与菌体内含硫的蛋白质、酶或简单分子相互作用，异噻唑啉酮化合物中S-N键断裂，其中的S与受体结合，形成S-S键，进一步与受体作用，可以夺取受体的氢，使受体-受体间形成S-S键，从而破坏细胞的正常功能阻碍核酸的形成，破坏菌体的生长和繁殖。此外，异噻唑啉酮类化合物能融化细胞壁，破坏了细胞内外环境的平衡，导致菌类死亡。反应式(2)所示的是异噻唑啉酮与菌体中谷胱甘肽(GSH)的作用过程，式中R5或R6为卤素、烷基或芳基；R7为H，烷 基、酰胺或酰氯。由反应式(2)可以看出R7位取代基的改变基本不会影响对异噻唑啉酮类化合物的抗菌活性，因此选择在R7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，第一部分是反应型苯并异噻唑啉酮杀菌剂的合成。在装有电动搅拌器、温度计的四口烧瓶中，加入适量的苯并异噻唑啉酮、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1-5h，将反应液倒入分液漏斗中，用蒸馏水洗涤3遍，加入无水硫酸钠干燥过夜，过滤除去硫酸钠，减压蒸馏得白色固体，即为反应型苯并异噻唑啉酮杀菌剂。
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，使苯并异噻唑啉酮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7.5g苯并异噻唑啉酮和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，再于室温下反应1h，将反应液倒入分液漏斗中，用蒸馏水洗涤3遍，加入无水硫酸钠干燥过夜，过滤除去硫酸钠，减压蒸馏得白色固体，即为反应型苯并异噻唑啉酮杀菌剂，产品收率94.6％。
将第一步中所得抗菌剂适量，壬基酚聚氧乙烯醚3g、聚氧乙烯醚失水山梨醇酯2.5g加入到95g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 | 98.2 | 424.6 |
| 10 | 97.0 | 423.9 |
| 15 | 97.2 | 424.1 |
| 20 | 97.2 | 424.2 |
表3水洗次数对抗菌率的影响
注：抗菌剂浓度为15％
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7.5g苯并异噻唑啉酮和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，再于40℃下反应2h，将反应液倒入分液漏斗中，用蒸馏水洗涤3遍，加入无水硫酸钠干燥过夜，过滤除去硫酸钠，减压蒸馏得白色固体，即为反应型苯并异噻唑啉酮杀菌剂，产品收率86.4％。
将第一步中所得抗菌剂12g，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90g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 | 97.6 | 423.2 |
| 10 | 97.0 | 423.5 |
| 15 | 96.4 | 423.1 |
| 20 | 96.1 | 422.8 |
表6水洗次数对抗菌率影响
注：抗菌剂浓度为15％ 。
Claims (1)
1.一种用于纺织品抗菌整理剂，其特征在于以苯并异噻唑啉酮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或R2为Cl，Br，F，NH2，NHCH3，NHCOCH3或R3或R4为H，CH3，CH2CH3，CH2CH2CH2CH3，Cl或Br。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310172543.7A CN103290678B (zh) | 2013-04-13 | 2013-04-13 | 一种用于纺织品抗菌整理剂 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310172543.7A CN103290678B (zh) | 2013-04-13 | 2013-04-13 | 一种用于纺织品抗菌整理剂 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103290678A CN103290678A (zh) | 2013-09-11 |
| CN103290678B true CN103290678B (zh) | 2015-07-22 |
Family
ID=49092173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310172543.7A Expired - Fee Related CN103290678B (zh) | 2013-04-13 | 2013-04-13 | 一种用于纺织品抗菌整理剂 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103290678B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264482B (zh) * | 2014-09-26 | 2016-11-30 | 枝江大江纺织有限责任公司 | 一种织物抗菌抗皱护理剂及其制备方法 |
| CN108385387A (zh) * | 2018-02-11 | 2018-08-10 | 芦山华美包纱有限公司 | 一种抗微生物纤维素纤维及生产方法及其应用 |
| CN111574654B (zh) * | 2019-10-21 | 2021-09-17 | 海南大学 | 一种含苯并[d]异噻唑啉-3-酮-三嗪基单体的丙烯酸酯防污树脂的结构及制备方法 |
| CN112301728A (zh) * | 2020-10-19 | 2021-02-02 | 山东魏桥特宽幅印染有限公司 | 一种抗菌面料及其印染工艺和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987004321A2 (en) * | 1986-01-23 | 1987-07-30 | Rhone-Poulenc Nederlands B.V. | Use of heterocyclic nitrogen-containing compounds for reducing moisture loss from plants and increasing crop yield |
| JPH05134348A (ja) * | 1991-11-15 | 1993-05-28 | Fuji Photo Film Co Ltd | ハロゲン化銀写真感光材料 |
| CN1725953A (zh) * | 2002-11-08 | 2006-01-25 | 兰克赛斯德国有限公司 | 杀微生物剂物质 |
| CN101175616A (zh) * | 2005-05-13 | 2008-05-07 | 朗盛德国有限责任公司 | 杀真菌混合物 |
| CN101254157A (zh) * | 2007-03-02 | 2008-09-03 | 高砂香料工业株式会社 | 防腐剂组合物 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0024529D0 (en) * | 2000-10-06 | 2000-11-22 | Avecia Ltd | Method and compositions |
-
2013
- 2013-04-13 CN CN201310172543.7A patent/CN103290678B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987004321A2 (en) * | 1986-01-23 | 1987-07-30 | Rhone-Poulenc Nederlands B.V. | Use of heterocyclic nitrogen-containing compounds for reducing moisture loss from plants and increasing crop yield |
| JPH05134348A (ja) * | 1991-11-15 | 1993-05-28 | Fuji Photo Film Co Ltd | ハロゲン化銀写真感光材料 |
| CN1725953A (zh) * | 2002-11-08 | 2006-01-25 | 兰克赛斯德国有限公司 | 杀微生物剂物质 |
| CN101175616A (zh) * | 2005-05-13 | 2008-05-07 | 朗盛德国有限责任公司 | 杀真菌混合物 |
| CN101254157A (zh) * | 2007-03-02 | 2008-09-03 | 高砂香料工业株式会社 | 防腐剂组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103290678A (zh) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Synthesis of novel reactive N-halamine precursors and application in antimicrobial cellulose | |
| Montazer et al. | Simultaneous x‐linking and antimicrobial finishing of cotton fabric | |
| CN103290678B (zh) | 一种用于纺织品抗菌整理剂 | |
| CN104396965B (zh) | 一种反应型卤胺抗菌剂及其制备方法和应用 | |
| US20030056297A1 (en) | Multifunctional textiles | |
| US20160138214A1 (en) | Antimicrobial finish on fabrics | |
| KR20140039480A (ko) | 항균성 셀룰로오스 섬유의 제조방법 및 이로부터 제조되는 섬유 | |
| CN104947418A (zh) | 一种壳聚糖季铵盐-银纳米微粒抗菌棉纤维的制备方法 | |
| CN102140764A (zh) | 一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法 | |
| CN107326654A (zh) | 一种针织面料的后整理工艺 | |
| CN105040430A (zh) | 一种涤纶印花布的新型抗菌后整理工艺 | |
| CN106149130B (zh) | 一种含银螯合腈纶纤维的可控抗菌毛巾及其制备方法 | |
| US20050011012A1 (en) | Multifunctional antimicrobial dyes | |
| CN103290679B (zh) | 一种含有三唑环的纺织品抗菌整理剂 | |
| CN104805697A (zh) | 一种新型棉织物用抗菌整理剂组合物 | |
| CN106906658A (zh) | 卤胺接枝天然纤维纺织品及其制备方法与应用 | |
| CN103265540A (zh) | 活性异噻唑啉酮类抗菌整理剂 | |
| CN107354750A (zh) | 一种抗菌羊毛制品及抗菌剂及其生产工艺 | |
| CN103061125A (zh) | 一种含有反应性官能团的卤胺类抗菌剂及其制备方法和应用 | |
| CN102154823A (zh) | 一种抗菌、防臭和杀菌纤维结构物的加工方法 | |
| CN105484064B (zh) | 一种卤胺类抗菌活性染料及其制备方法和应用 | |
| US3749788A (en) | Microbicidal and germicidal compositions containing n-halophenyldichloroisothiazolones | |
| CN100371525C (zh) | 纳米会呼吸多功能面料的制备方法 | |
| CN115478435B (zh) | 一种织物用水性长效防霉剂及其制备方法 | |
| JP2001288015A (ja) | 抗菌・抗カビ加工用ピリチオン亜鉛含有分散液及び該分散液を用いた繊維類の抗菌・抗カビ加工方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: XU MAOHANG Free format text: FORMER OWNER: LI MEIFENG Effective date: 20150619 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Maohang Inventor before: Li Meifeng |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LI MEIFENG TO: XU MAOHANG |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150619 Address after: Licang District of Shandong province 266000 fo Lu Zheng Qingdao City No. 17 Applicant after: Xu Maohang Address before: 266071 building 306, No. 10, Ningxia Road, Shandong, Qingdao Applicant before: Li Meifeng |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Lin Inventor before: Xu Maohang |
|
| COR | Change of bibliographic data | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160928 Address after: 266000 Licang, Qingdao, No. nine East water road, No. 320, No. Patentee after: Qingdao one card Trading Co., Ltd. Address before: Licang District of Shandong province 266000 fo Lu Zheng Qingdao City No. 17 Patentee before: Xu Maohang |
|
| CB03 | Change of inventor or designer information |
Inventor after: Xu Maohang Inventor before: Zhang Lin |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180111 Address after: Licang District of Shandong province 266000 fo Lu Zheng Qingdao City No. 17 Patentee after: Xu Maohang Address before: 266000 Licang, Qingdao, No. nine East water road, No. 320, No. Patentee before: Qingdao one card Trading Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181123 Address after: 314200 No. 118 West Side of Caoqiao Street Caojiu Highway, Pinghu City, Jiaxing City, Zhejiang Province Patentee after: Zhejiang Jingye Dyeing and Finishing Co., Ltd. Address before: 266000 zhengbuddha Road, Licang District, Qingdao, Shandong Province, No. 17 Patentee before: Xu Maohang |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 Termination date: 20190413 |