WO2012113093A1 - 一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法 - Google Patents

一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法 Download PDF

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WO2012113093A1
WO2012113093A1 PCT/CN2011/000269 CN2011000269W WO2012113093A1 WO 2012113093 A1 WO2012113093 A1 WO 2012113093A1 CN 2011000269 W CN2011000269 W CN 2011000269W WO 2012113093 A1 WO2012113093 A1 WO 2012113093A1
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group
antibacterial
deodorant
fibrous structure
acid
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PCT/CN2011/000269
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English (en)
French (fr)
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李民旭
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上海优益基医药技术有限公司
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Priority to PCT/CN2011/000269 priority Critical patent/WO2012113093A1/zh
Publication of WO2012113093A1 publication Critical patent/WO2012113093A1/zh

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35Heterocyclic compounds
    • D06M13/355Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358Triazines
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005Compositions containing perfumes; Compositions containing deodorants
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325Amines
    • D06M13/335Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

Definitions

  • the invention belongs to the technical field of textile printing and dyeing, and relates to a method for imparting antibacterial, deodorizing and anti-viral functions to a fibrous structure, in particular to a dihalotriazine sodium salt having a hydrophilic substituent, an aromatic amine compound and having Under the condition of coexistence of hydrophilic organic antibacterial, deodorant and anti-toxic agents, heat treatment is carried out by using an impregnation method (PAD DRY) or a dipping method (bath exhaustion method) at 30 to 90 ° C to impart the fiber structure.
  • PID DRY impregnation method
  • bath exhaustion method bath exhaustion method
  • Influenza A (H1N1), which was originally transmitted only among animals, has been widely recognized by the World Health Organization because of the sudden mutation of the virus, the spread of avian flu worldwide and the death of many people. If the avian flu epidemic breaks out, it is likely to cause incalculable losses to the ecological environment, the economy and humans, and even the catastrophe. After the first MRSA (ie methicillin-resistant Staphylococcus aureus) was discovered in the UK in 1961, this so-called super virus was spreading at an alarming rate. Judging from the current medical knowledge, this superbug is highly likely to be prevalent throughout the world and is resistant to more and more antibiotics.
  • MRSA methicillin-resistant Staphylococcus aureus
  • hypochlorous acid disinfection technology manufactured by electrolytically replenishing saline; ozone sterilization technology utilizing the principle of electrostatic discharge; and ultraviolet sterilization technology have been commercialized.
  • chlorine or hypochlorous acid contained in the residual liquid of the disinfectant has side effects such as irritating odor, and there are reports that there may be a safety hazard.
  • the society such as universities and pharmaceutical companies, work together to develop fiber products with antibacterial, deodorant and antiviral functions, so that the bacterial viruses stained on the fiber products are inactivated.
  • the post-treatment method is to impregnate, pad or coat the fabric with a solution or resin containing an antibacterial agent.
  • a solution or resin containing an antibacterial agent When evaporating by high temperature baking or other methods, an insoluble or slightly soluble antibacterial agent is deposited on the fabric. , so that the fabric obtains antibacterial properties.
  • it is processed in the final stage of dyeing and finishing, and can also be processed after being finished, to obtain a dissolution-type antibacterial textile and a non-dissolving antibacterial textile.
  • Dissolved antibacterial textiles are textiles that can diffuse from the inside to the surface of the fiber to form an antibacterial ring, thereby killing bacteria in the ring. These types of textiles have poor washability.
  • Non-dissolving antibacterial textiles are generally obtained by chemically reacting a surface having an antibacterial property on the surface of the fibrous structure, and these antibacterial agents can form covalent bonds or ions with the fibrous structure.
  • the antibacterial agent cannot be diffused when it is applied, but the bacteria in contact with the fibrous structure can be killed, and the antibacterial effect is long lasting.
  • the raw silk improvement processing method is to mix an auxiliary agent such as an antibacterial agent and a dispersing agent with a fiber structure base resin, and to produce a fiber structure having antibacterial properties by melt spinning.
  • This method is mainly for some fiber structures without reactive side groups, such as polyester, polypropylene, etc.; the antibacterial agent not only exists on the surface of the fiber structure, but also uniformly dispersed in the fiber structure, and the antibacterial effect is relatively long-lasting.
  • the fiber structure containing the antibacterial component is conjugated with another fiber structure or a fiber structure containing no antibacterial component to form an antibacterial fiber structure of a side-by-side type, a core-sheath type, a mosaic type, and a hollow multi-core structure.
  • the technical solution adopted is: a method for imparting antibacterial, deodorizing and anti-viral functions to the fibrous structure, including impregnation or impregnation of the fibrous structure at an initial temperature of less than 30 ⁇ of the dyeing aqueous solution, the characteristics of which are characterized by 5 to 10 minutes.
  • the pH is 8. 0 ⁇ 13.
  • the pH is 8. 0 ⁇ 13.
  • the pH is 8. 0 ⁇ 13.
  • heat treatment is carried out by using an impregnation method (PAD DRY) or a dipping method (bath exhaustion method) at a temperature of 30 ⁇ to 90 Torr.
  • the molecular structure of the fiber structure has the characteristics of an amino group (- ⁇ 2), a hydroxyl group (-0 ⁇ ), or a carboxyl group (-C00H), and imparts an efficient, durable antibacterial, deodorant, and antiviral function to the fiber structure.
  • the dihalotriazine sodium salt having a hydrophilic substituent in the present invention is a 2,6-dihalogen-4-y-1,3,5-triazine derivative, as in the formula (1) Show.
  • X refers to a halogen group selected from the group consisting of chlorine, fluorine and bromine
  • Y means at least one group selected from the group consisting of a sulfo group, a carboxyl group, a hydroxide group and a thiol group. Substituted by amino, aryloxy, arylhydrazine, decylamino, decyloxy, sulfonylthio, triazinylamino, triazinyloxy, triazinethio.
  • the above sulfo group, carboxyl group, hydroxide group, and hydrogen atom in the thiol group may be substituted by an alkali metal atom or an alkaline earth metal atom.
  • the above 2,6-dihalo-4-y-1,3,5-triazine derivative means at least one of the following compounds:
  • the aromatic amine compound mentioned in the present invention is one of aromatic amine compounds in which a benzene ring is bonded to N of one or more amine groups.
  • the following various compounds are mentioned as an aromatic amine compound.
  • Phenylenediamine sulfonate Li, Na, K
  • the organic antibacterial, deodorant and anti-toxic agent described in the present invention is one of the following compounds:
  • Carbohydrates include: chitosan, hydroxypropyl ester chitosan, bridging chitosan, chitosan organic acid bismuth, caramel micropowder, chitin fiber, chitin.
  • Phenol ketones are: cedar phenol, cypress oil emulsion, haiba oil, a mixture of cyclodextrin and haiba oil, haiba oil emulsion.
  • the esters are: undecylenic acid monoglyceride, fatty acid glyceride, fatty acid ester acid, glycerin fatty acid ester, Polyethylene glycol methyl ether methacrylate perfluorophosphonium phosphate, phosphate polymer.
  • Terpenes are: 1, 8- eucalyptus (Peng tree, eucalyptus, lemon eucalyptus)
  • the benzoic acid is: a complex of polymethacrylic acid, polyacrylate and lead sulfate, nalidixic acid: 1-ethyl- 1, 4-dihydro-7-methyl-4-oxo-1. 8-naphthyridine-3-benzoic acid
  • the biguanides are: chlorhexidine gluconate, acidification inhibition of picoester, PHMB hydrochloride, chlorhexidine and 2 acrylamide 2 methylpropanal sulfonic acid co-reclosure, PHMB polychloroborite and lead oxide Complex quaternary ammonium salts: dodecyltrimethylammonium chloride, hexadecanyltrimethylammonium chloride, BS-12 betaine, amine oxide, dimethyldioctadecyl ammonium chloride, Dodecyl dimethylbenzyl chloride hinge, octadecyl, dimethylbenzylammonium chloride, octadecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, double Octyl dimethyl ammonium chloride, bis-decyl dimethyl ammonium chloride, diddecyl dimethyl ammonium chloride, dodecyl dimethyl am
  • Organic solvents Triclosan, Triclosan and naphthyridine (keto) acid formulations, aniline amphoteric surfactants: mercaptoamide propyl dimethyl-hydroxy ether ammonium salt, polyethylene oxide
  • aniline amphoteric surfactants mercaptoamide propyl dimethyl-hydroxy ether ammonium salt, polyethylene oxide
  • Neodymium borosilicate Amino acid: N-decanoyl-L-2-aminoglutaric acid silver copper
  • Sulfonamides are: N, N-dimethyl-N-(dichlorofluoromethylthio)-N'-phenylsulfonamide
  • Pyridine bis(2-pyridinethiol-lead-1-oxide) lead, bis(1-hydroxy-2(1)pyridinethiosulfate (0, S)-T-4)
  • Nitrile 2, 3, 5, 6 tetrachloroisophthalonitrile
  • Polymer Acrylic acid, copolymerized copper bridge of acryl acid, copper acrylate copper sulphate, acrylamido allylamamine hydrochloride copolymer, methacrylate copolymer.
  • lactoferrin lactoferrin
  • lactoferrin antibacterial peptide
  • dichloromethane lactoferrin, lactoferrin, antibacterial peptide, dichloromethane
  • the drying process of the fiber structure is carried out at a temperature of 6 (TC-90 ° C, and various dryers can be used, and the drying time is about 3 minutes to 20 minutes.
  • Rapid heating not only leads to dihalotriazine sodium salts with hydrophilic substituents, aromatic amine compounds, and hydrophilic organic, organic or organic antibacterial, deodorant and anti-toxic agents in the CH3 group (H) It cannot be effectively combined, and the (H) molecule in the fiber material cannot be effectively combined or chlorinated.
  • the temperature increase rate is preferably controlled to be 2 ° C / min or less.
  • the present invention is applicable to a fibrous structure having an amino group (-NH2), a hydroxyl group (-0H), and a carboxyl group (-C00H).
  • a fibrous structure having an amino group (-NH2), a hydroxyl group (-0H), and a carboxyl group (-C00H).
  • natural materials such as silk, wool, cotton, hemp, and recycled fibers such as rayon, polyester, and nylon. It can also be applied to leather, feathers, etc.
  • These fibrous structures are characterized by a substitutable (H) molecule.
  • the reaction principle is a dihalotriazine sodium salt having a hydrophilic substituent, an aromatic amine compound, and an organic antibacterial, deodorant and anti-toxic agent having hydrophilicity, and undergoing molecular bonding or chlorination due to electron exchange, and
  • the triazine ring of the fiber material combines to form an antibacterial, deodorant, and antiviral function with high efficiency and durability.
  • the beneficial effects of the present invention are as follows:
  • the method of the invention is simple, and as long as there is a dyeing machine and a dryer, a fibrous structure having antibacterial, deodorant and antiviral effects can be produced.
  • the fiber structure processed by the invention is durable against bacteria, odor and anti-virus, and can meet the demand for manufacturing medical care products, and is suitable for mass production.
  • the fibrous structure processed by the present invention can be applied to fiber products in various fields such as medical treatment, clothing, and bedding.
  • Specific examples can include: suits, sportswear, jackets, pants, skirts, uniforms, etc., swimwear, socks, shoes, slippers, underwear, bras, etc.
  • Shoes white coats, surgical gowns, aprons, wet diapers, Medical care products such as sanitary napkins, bedding, pillows, duvet covers, blankets and other bedding, ropes, bags, gloves, crepe, tablecloths, saddles, carpets, curtains, wallpapers and other industrial supplies, various materials made of leather fiber materials.
  • the invention provides a method for imparting antibacterial, deodorizing and anti-viral functions to a fiber structure.
  • the fiber structure is impregnated or impregnated for 5 to 10 minutes, and the dyeing aqueous solution has a hydrophilic substituent.
  • Antibacterial and anti-bacterial of dihalotriazine sodium salt, aromatic amine compound and hydrophilic organic substance coexist, and the pH is adjusted to be 0. 0 to 13. 0, and the heat treatment is performed by an impregnation method (PAD DRY) or a dipping method (bath exhaustion method) at an environment of 30 ° C to 90 ° C.
  • the use of dyeing machines includes jiggers, flow dyeing machines, beam dyeing machines, and the like.
  • the bath ratio is required to be 1:60 or less.
  • the initial temperature of the liquid is required to be below 30 °C. 01% ⁇ 10% (0. W)
  • the temperature is required to raise the temperature to 60 ° C in a uniform temperature within 20 to 30 minutes.
  • the speed is approximately rC ⁇ 2O/min.
  • the first reaction is carried out, and the first reactive chlorine group of the dihalotriazine sodium salt having a hydrophilic substituent in an alkaline environment is bonded to the amino group of the aromatic amine compound to form a new compound. .
  • the CH3 group of the hydrophilic organic antibacterial, deodorant and anti-toxic agent will undergo electron displacement reaction with OH-CH2 to form a new compound and sodium chloride. If the temperature is rapidly increased, the chlorine group of the dihalotriazine sodium salt having a hydrophilic substituent is decomposed, and an effective electron displacement reaction cannot be performed.
  • the second temperature-increasing treatment requires a temperature between 60T: and 90 ⁇ , and the second reactive chlorine group of the dihalotriazine sodium salt having a hydrophilic substituent will be associated with (-NH-) in the amino fiber-containing structure or (-0-) in the alcohol-containing hydroxy fiber structure or (-C00-) in the carboxyl group-containing structure is subjected to a common binding reaction.
  • the necessary conditions for the reaction are temperature between 601: ⁇ 9 CTC for 30 to 90 minutes. Then, after cold water washing, hot water washing, acid neutralization and drying, the fibrous structure will have high-efficiency, durable antibacterial, deodorizing and anti-viral functions.
  • the heat treatment is carried out at 30 ° C to 9 (in the TC environment, including heat treatment and continuous heat treatment.
  • Specific embodiments are given below to disclose the most preferred embodiment of the present invention, which is intended to enable those skilled in the art. It is to be understood that the present invention is not limited by the embodiments of the present invention. It is to be understood that the present invention is not limited by the embodiments. Any obvious alterations or substitutions should also be considered within the scope of the present invention. Inside.
  • the water temperature of the dyeing aqueous solution was controlled at 25 ° C, and 4 ml of 2,6-dichloro-4-sulfo-R-triazine Na salt of 45 ml and 2,6-dichloro-4-ureido group were added at a concentration of 10% each.
  • - R-triazine aqueous solution 45 ml, the input concentration is 1% (0. W. S) of 3, 3 '-dimethoxybenzidine 30 ml, mixed and stirred to prepare a preparation; 50 ml of this preparation was put into a glass container, and 10 g of sodium carbonate and 15 g of carbonic acid were charged.
  • the water temperature of the dyeing aqueous solution is controlled to a concentration of 5% in a 100% aqueous solution of 10% 2,6-dichloro-4-(3-5-disulfophenylamino)-R-triazine in an aqueous solution of 25 Torr. (0. W. S) 4, 4'-diamino-.3,3'-dichlorodibenzopyridinyl 30 ml, mixed and mixed to prepare a preparation; 15 ml of this preparation is put into a glass container, put 20 g of sodium carbonate, the pH was adjusted to 10.2, and then 2 ml of a solution containing 80% of glycerin fatty acid ester was poured and stirred.
  • the water temperature of the dyeing aqueous solution is controlled to a concentration of 10% (0. W) in an aqueous solution of 10% 2,6-dichloro-4-(4-carboxyanilino)-R-triazine at 25 ° C.
  • the water temperature is controlled to a concentration of 10% 2,6-dichloro-4-hydroxy-R-triazine Na salt at 25 ° C.
  • a concentration of 5% (0. W. S) of sodium 2,4'-diaminobenzenesulfonate was added and mixed to prepare a preparation; 8 ml of the preparation was placed in a glass container, and 10 g of sodium sulfate was added thereto.
  • JIS white cloth standard white cloth
  • the temperature was gradually raised to 60 Torr over a period of 20 minutes, and then the temperature was raised to 80 V by an electric heating furnace, and the temperature was stirred at 80 ° C for 30 minutes.
  • drain, wash for 5 minutes neutralize in water at 50 °C for 15 minutes, then drain and wash. Then, it is dried using a conventional softener.
  • the temperature of the aqueous solution was raised to 60 ° C at a rate of 1.5 ° C / min for 20 minutes, and then the temperature was raised to 80 ° C for 15 minutes, and the water was stirred for 30 minutes, and then drained, and water was poured.
  • the acid neutralization treatment was carried out for 10 minutes in the water temperature of °C, and then washed and washed, and dried by a conventional softener.
  • the temperature of the aqueous solution was raised to 60 Torr at a rate of 1.5 ° C / min for 20 minutes, and then heated to 80 Torr for 15 minutes. The temperature was kept at 80 Torr for 30 minutes, drained, and water was injected at 40 Torr. After 10 minutes of acid neutralization, it is cleaned again after draining and dried with a traditional softener.
  • the temperature of the aqueous solution was raised to 60 ° C at a rate of 1.5 ° C / min for 20 minutes, and then heated to 80 ° C for 15 minutes, and kept at a water temperature of 80 ° C for 30 minutes, drained, and filled with water. , acid neutralization treatment was carried out for 10 minutes at 40 ° C water temperature, washed again after draining, and finally, dried by a conventional softener.
  • the temperature of the aqueous solution was raised to 60 ° C at a rate of 1.5 ⁇ / min for 20 minutes, and then heated to 8 (TC for 15 minutes), and drained after 8 minutes of heat preservation in the water temperature of TC.
  • acid neutralization treatment was carried out for 10 minutes at a water temperature of 40 ° C, washed again after draining, and finally, dried by a conventional softener.
  • the cotton cloth processed by the method of the present invention was entrusted to Kyoto Prefectural Medical University in Japan to inactivate the avian influenza virus by using the JIS L-1902 bacterial liquid exhaustion method.
  • the average antiviral rate of the avian influenza virus was 99.87%.
  • the same test was carried out on the same sample, and the average antiviral rate of the avian influenza virus was 99.92%, which proved the processing method of the present invention. Has a lasting effect.
  • the test results are shown in Table 1.
  • Table 1 Test unit Kyoto Prefectural University PFU/mL virus reduction rate unprocessed standard white cloth 1. 61 X 105
  • the processed cotton was subjected to MRSA (Methici 11 in-Resistant Staphylococcus Aureus) LLD 1677 antibacterial test by the JIS L-1902 bacterial liquid exhaustion method by the Japan Chemical Fiber Association Biological Testing Center. It was proved that the processing method has a bactericidal effect on the bacterium.
  • MRSA Metal 11 in-Resistant Staphylococcus Aureus
  • Test unit Biological Testing Center of Chemical Fiber Inspection Association of Japan
  • the JIS L-1902 bacterial liquid exhaustion method was used by the Biochemical Testing Center of the Japan Chemical Fiber Association to perform the antibacterial test of Staphylococcus aureus on the processed wool fabric. It was confirmed that the processing method has an antibacterial effect on the bacterium.
  • the test results are shown in Table 3.
  • Antibacterial and deodorant standards Static bacteria activity value 2. 2 or more
  • ⁇ Pathogen Staphylococcus aureus ATCC 6538P
  • the fiber product treated by the processing method of the present invention has an efficient, long-lasting antibacterial, deodorant, and antiviral effect.

Description

一种赋予纤维结构物抗菌、 防臭及抗病毒功能的方法
技术领域
本发明属纺织印染技术领域,涉及一种赋予纤维结构物抗菌、防臭及抗病毒功能 的方法,特别涉及一种在具有亲水性取代基的二卤代三嗪钠盐、芳香胺化合物以 及具有亲水性的有机类的抗菌、防臭及杀毒剂共存条件下,利用含浸法(PAD DRY) 或浸渍法 (浴中吸尽法) 在 30〜90°C环境下热处理, 赋予所述纤维结构物具有 高效、 耐久的抗菌、 防臭及抗病毒功能的加工方法。 背景技术
本来只有在动物间传染的甲型 H1N1流感, 由于病毒的突然变异, 禽流感在全球 蔓延并导致了很多人的死亡, 已引起世界卫生组织的高度重视。如果禽流感流行 爆发的话, 很有可能对生态环境、经济以及人类造成不可估计的损失, 甚至是灾 难性的打击。 1961年英国发现首例 MRSA (即耐甲氧西林金黄色葡萄球菌)之后, 这种所谓的超级病毒正以惊人的速度传布蔓延。从目前掌握的医学知识来看,这 种超级病菌极有可能在全世界范围内流行, 并对越来越多的抗生素产生抗药性。 通过电解精制食盐水制造的次氯酸消毒技术; 利用静电放电原理的臭氧杀菌技 术; 以及紫外线杀菌技术等都已经被产品化。但是在消毒液的残液中含有的氯或 次氯酸, 具有刺激性气味等副作用, 并有报道说可能存在安全隐患。
作为对策之一, 由大学、 制药公司等社会各界共同努力, 研制开发有抗菌、 防臭 及抗病毒功能的纤维制品, 使纤维制品上染上的细菌病毒失去活性。
关于纤维制品的抗菌加工方法, 通常有后处理加工法与原丝改良加工法两种。 后处理加工法是利用含抗菌剂的溶液或树脂对织物进行浸渍、 浸轧或涂覆处理, 在通过高温焙烘或其他方法蒸发时, 织物上就会沉淀一层不溶或微溶的抗菌剂, 从而使织物获得抗菌性能。一般在染整加工最后阶段迸行处理, 也可在制成成品 以后处理,制得溶出型抗菌纺织品和非溶出型抗菌紡织品。溶出型抗菌纺织品是 指可以从内部扩散到纤维表面形成抗菌环,从而杀死环内细菌的纺织品。这类纺 织品耐洗性不好。非溶出型抗菌纺织品一般通过化学反应在纤维结构物表面接上 具有抗菌性能的基团而获得, 这些抗菌剂可以与纤维结构物形成共价键或离子
1
确认本 键, 作用时抗菌剂不能扩散, 但与该纤维结构物接触的细菌均可被杀灭, 而且抗 菌效果较为持久。
原丝改良加工法是将抗菌剂和分散剂等助剂与纤维结构物基体树脂混合,通过熔 融纺丝生产出具有抗菌性能的纤维结构物。这种方法主要针对一些没有反应性侧 基的纤维结构物, 如涤纶、 丙纶等; 抗菌剂不仅存在于纤维结构物的表面, 而且 均匀分散于纤维结构物中, 抗菌效果比较持久。利用含有抗菌成分的纤维结构物 与其它纤维结构物或者不含抗菌成分的纤维结构物复合纺丝,制成并列型、芯鞘 型、 镶嵌型、 中空多心型结构的抗菌纤维结构物。
但是,上述加工方法,多数利用树脂或硅氧垸等含有甲醛等含有致癌物质的助剂, 在健康上存在安全隐患。而且在处理后的排水中残留药物以及 B0D (生化需氧量) 等指标上也存在问题。
发明内容
本发明的目的是提供简单、 安全、环保的一种赋予纤维结构物抗菌、 防臭及抗病 毒功能的方法。
为达到上述目的, 采用的技术方案是: 一种赋予纤维结构物抗菌、 防臭及抗病毒 功能的方法, 包括染色水溶液初始温度低于 30Ό时投入纤维结构物含浸或浸渍 5〜10分钟, 其特征在于: 染色水溶液中具有亲水性取代基的二卤代三嗪钠盐、 芳香胺化合物以及具有亲水性的有机类的抗菌、 防臭及杀毒剂共存, 调节 pH值 为 8. 0〜13. 0, 并利用含浸法 (PAD DRY) 或浸渍法 (浴中吸尽法) 缓慢升温在 30 Ό〜90 Ό度环境下进行热处理。 利用纤维结构物的分子构成中具有氨基 (-ΝΗ2)、 羟基(-0Η)、 或羧基(- C00H) 的特性, 赋予纤维结构物具有高效、 耐 久的抗菌、 防臭及抗病毒的功能。
本发明中具有亲水^取代基的二卤代三嗪类钠盐为 2, 6-二卤代 - 4-Y-1 , 3, 5 - 三嗪衍生物, 如通式( 1 )中所示。
Y
I
N N 通式(1 ) 中, X指的是氯, 氟以及溴类中选出来的卤素基, Y指的是由磺基、 羧 基、氢氧根以及硫醇基类中至少选出一种基被芳氨基、芳氧基、芳巯基、垸氨基、 垸氧基、 垸硫基、 三嗪氨基、 三嗪氧基、 三嗪硫基所取代。
上述的磺基、羧基、氢氧根, 以及硫醇基中的氢原子也可以被碱性金属原子或者 是碱土金属原子取代。
在本发明中, 上述 2, 6-二卤代 - 4-Y-1 , 3, 5-三嗪衍生物是指含有以下化合物 中的至少一种物质:
2, 6-二氯 -4-硫 -R-三嗪 Na盐
2, 6-二氯- 4- ( 3-磺基苯胺基) - R -三嗪 Na盐
4, 4-二 (4, 6-二氯- R-三嗪- 2- ylamino) 均二苯代乙烯 -2, 2, -二磺酸 Na盐
2, 6-二氯- 4- ( 3-磺基苯胺基) - R-三嗪
2, 6-二氯- 4- (4-磺基苯胺基) - R-三嗪
2, 6-二氯- 4- ( 2, 5-二磺基苯胺基) - R-三嗪
2, 6-二氯 -4- ( 3-5-二磺基苯胺基) -R-三嗪
2, 6-二氯 -4- ( 3-羧基苯胺基) - R-三嗪
2, 6-二氯 -4- (4-羧基苯胺基) - R-三嗪
2, 6-二氯- 4- ( 2-羧基苯胺基) - R-三嗪
2, 6-二氯 -4- ( β -羧基乙基氨基) -R-三嗪
2, 6-二氯- 4-脲基 -R-三嗪
2, 6-二氯 -4-硫代脲基- R-三嗪
2, 6-二氯 -4- (4-羧基苯氧基) -R-三嗪
2, 6-二氯- 4- ( 4-羧基苯硫基) -R-三嗪
2, 6-二氯 -4-羟基- R-三嗪 Na盐
2, 6-二氯 -4-羟基- R -三嗪 Li盐
2, 6-二氯- 4-羟基 -R-三嗪 Mg盐
本发明中所提到的芳香胺化合物为苯环与一个或者多个胺基的 N相连的芳香胺 化合物的一种。 作为芳香胺化合物可列举以下多种化合物。
4, 4 ' - 氨基联苯 3, 3' - 二甲氧基联苯胺
3, 3' - 二氯联苯胺
4, 4' - 二氨基 - 3, 3' - 二氯二苯甲垸基
4, 4' - 二氨基二苯甲垸基
4, 4' - 二氨基 - 5, 5' - 二甲基连苯基 - 2, 2' - 二磺酸
3/3' - 二甲基 - 4, 4' - 二氨二苯基 - 5, 5' - 二磺酸
氨基联苯 - 2, 2' - 二磺酸
4, 4' - 磺酰二苯胺
氨基联苯- 3, 3' - 二苯甲酸 - 3, 3' - 二羧基氨基联苯
5, 5' - 亚甲基二氨茴酸
4, 4' - 二氨基二苯胺基 - 2 -磺酸
4, 4' - 二氨基二苯硫醚
4, 4' - 二氨基二苯砜
3, 3' - 二氨基二苯砜
4, 4' - 羟基二苯胺
2, 4' 一 二氨基苯磺酸钠
4, 6 - 苯二胺 - 1, 3-二磺酸
苯二胺磺酸盐 (Li,Na,K)
3, 5 - 二氨基苯甲酸
3, 4 ― 二氨基苯甲酸
1, 4 - 二氨基蒽醌 - 2, 3 - 二磺酸
1, 4 - 二氨基蒽醌
本发明中所述具有亲水性的有机类的抗菌、 防臭及杀毒剂为如下化合物中的一 种:
碳水化合物类有: 甲壳糖、 羟丙基酯甲壳糖、 架桥甲壳糖、 甲壳糖有機酸塩、 甲 壳糖微粉末、 甲壳质纤维、 甲壳质。
酚酮类有: 扁柏酚、 日柏油乳剂、 亥巴油、 环化糊精类和亥巴油的混合物、 亥巴 油乳剂。
酯类有: 十一碳烯酸单酸甘油酯、 脂肪酸甘油酯、 脂肪酸酯酸、 甘油脂肪酸酯、 聚乙二醇甲醚异丁烯酸盐全氟垸磷酸酯、 磷酸酯类聚合物。
萜烯类有: 1, 8-桉树脑 (蓬树、 桉树、 柠檬桉树)
苯甲酸类有: 聚甲基丙烯酸、 聚丙烯酸盐和硫酸亚铅的配合物、 萘啶酮酸: 1-乙 基- 1, 4-二氢- 7-甲基- 4-氧代- 1 , 8-萘啶- 3-苯甲酸
醇类有: 多元 类化合物
双胍类有: 葡萄糖酸洗必泰、 皮酯酸化抑制、 PHMB盐酸盐、 氯洗必泰和 2丙烯 酰胺 2甲基丙醛磺酸的共重合体、 PHMB多水氯硼钙石和氧化亚铅的配合物 季胺盐类: 十二垸基三甲基氯化铵、 十六垸基三甲基氯化铵、 BS-12甜菜碱、 氧 化胺、 氯化二甲基双十八烷基铵、 十二垸基二甲基苄基氯化铰、 十八烷基、 二甲 基苄基氯化铵、十八垸基三甲基氯化铵、十四垸基三甲基氯化铵、双辛烷基二甲 基氯化铵、双壬垸基二甲基氯化铵、双十垸基二甲基氯化铵、双十二烷基二甲基 氯化铵、双十四烷基二甲基氯化铵、双十六垸基二甲基氯化铵、双十八垸基二甲 基氯化铵 ^
有机溶剂类: 三氯卡斑、 三氯卡斑与萘啶 (酮) 酸的调配物、 苯胺类化合物 两性界面活性剂: 垸基酰胺丙基二甲基 -羟基醚铵盐、 聚环氧乙垸氯硼钙石 : 氨基酸: N-垸酰基 -L-2—氨基戊二酸酸銀銅
磺酰胺类有: N, N-二甲基 -N- (二氯氟甲硫基) -N' -苯基磺酰胺
吡啶: 二 (2-吡啶硫醇-亚铅 -1-氧化物) 亚铅、 二 (1-羟基 -2 ( 1 ) 吡啶硫代硫 酸盐 ( 0, S ) -T-4 ) 亚铅
腈: 2, 3, 5, 6四氯异苯二甲腈
聚合物: 丙烯腈酸、 丙烯酰基酸的共聚合物铜架桥物、 丙烯腈酸硫化铜合成物、 丙烯腈酸酰氨基烯丙胺盐酸盐共聚合物、 异丁烯酸盐共聚合物。
其它: 乳铁传递蛋白、 乳铁蛋白、 抗菌性缩氨酸、 二氯甲垸
为了使上述物质在碱性溶液中共存, 调制时需要加入从氢氧化钠, 碳酸钠、碳酸 氢钠、 或硫酸钠中选出的至少一种物质, 使 pH值达到 8. 0〜13. 0之间。
[PAD . DRY法]: 在 6(TC—90°C的温度下进行纤维结构物的烘干工艺, 可以利用 各种烘干机, 烘干时间大约是在 3分到 20分之间。
[浴中吸尽法]: 在 30°C—9(TC的温度下进行加工处理, 可以使用液流染色机、 卷染机、绳装染色机以及成衣染色机等。几乎可以在与染色时的相同条件下进行 加工。 第一次热处理是利用 20〜30分钟的时间慢慢的升温到 30'C— 60Ό ; 第二 次热处理是利用 30〜60分钟的时间慢慢的升温到 60°C— 90°C。 急速升温不仅导 致具有亲水性取代基的二卤代三嗪钠盐、芳香胺化合物以及具有亲水性的天然有 机类或有机类的抗菌、 防臭及杀毒剂中 CH3基中的 (H) 分子不能有效结合, 而 且也不能让纤维材料中的 (H) 分子进行有效结合或进行氯化反应。 升温速度最 好控制在 2°C/分以下。
本发明适用于具有氨基 (- NH2 ), 羟基 (-0H) , 羧基 (- C00H)的纤维结构物。 如, 真丝、 毛、 棉、 麻等天然素材以及人造丝、 涤、 尼龙等再生纤维。 也可应用于皮 革、 羽毛等。 这些纤维结构物的特点是具有可取代的 (H)分子。
反应原理是具有亲水性取代基的二卤代三嗪钠盐、芳香胺化合物以及具有亲水性 的有机类的抗菌、 防臭及杀毒剂, 由于电子交换而进行分子结合或氯化反应, 与 纤维材料的三嗪环结合而构成具有高效性、 耐久性的抗菌、 防臭及抗病毒功能。 本发明的有益效果是: 本发明方法简单, 只要有染色机与烘干机, 即可生产出具 有抗菌、防臭及抗病毒效果的纤维结构物。生产过程中不存在残留氯素或次氯素 问题, 也没有利用树脂或硅酸, 不存在甲醛(福尔马林) 问题, 更不需要长期的. 紫外线照射, 因而对人类健康、环境保护都将起到积极的作用。本发明加工的纤 维结构物抗菌、 防臭及抗病毒功能耐久, 可以满足制作医疔护理用品需求, 适合 大规模生产。
本发明加工的纤维结构物, 可以应用在医疗, 服装, 床上用品等各个领域的纤维 制品上。 具体的列举可以包括: 西服、 运动服、 夹克衫、 裤子、 裙子, 制服等外 装类, 泳装、 袜子、 鞋、 拖鞋、 内衣、 胸罩等鞋子内衣类, 白大褂、 手术服、 围 裙、 尿布湿、 卫生巾等医疗看护用品, 被子、 枕头、 被套、 毛毯等床上用品, 绳 索、 包、 手套、 苫布、 桌布、 车座、 地毯、 窗帘、 壁纸等工业用品, 皮纤维材料 制作的各种用品。 具体实施方式
本发明一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法, 染色水溶液初始温 度低于 30°C时投入纤维结构物含浸或浸渍 5〜10分钟, 染色水溶液中具有亲水 性取代基的二卤代三嗪钠盐、芳香胺化合物以及具有亲水性的有机类的抗菌、防 臭及杀毒剂共存, 调节 pH值为 8. 0〜13. 0, 并利用含浸法 (PAD DRY) 或浸渍法 (浴中吸尽法) 在 30°C〜90°C度环境下进行热处理。
以下以浴中吸尽法为例, 对本发明作进一步说明。
使用染色机包括卷染机, 液流染色机, 束状染色机等。 浴比要求在 1: 60以下。 液体的最初温度要求在 30°C以下。 具有亲水性取代基的二卤代三嗪钠盐、 芳香 胺化合物、 以及具有亲水性的有机类的抗菌、 防臭及杀毒剂, 浓度要求分别是 0. 01%〜10% (0. W. S), 加入氢氧化钠, 或碳酸钠、 或碳酸氢钠中至少一种, 或加 入适当的硫酸钠, 将溶液的 pH值调整到 8. 0-13. 0。 在 30°C的温度下运转 5〜10 分钟, 让溶液完全渗入纤维结构物中, 然后进行第一次升温, 缓慢升温是必要条 件, 要求在 20〜30分钟内匀速升温到 60°C, 升温速度大约是 rC〜2O/分钟。 此时进行第一次反应,在碱性环境下具有亲水性取代基的二卤代三嗪钠盐的第一 反应氯基将与芳香胺化合物的氨基进行 0H-NH结合, 形成新的化合物。具有亲水 性的有机类的抗菌、 防臭及杀毒剂的 CH3基将与 OH- CH2进行电子置换反应形成 新的化合物与氯化钠。如果急速升温的话,将导致具有亲水性取代基的二卤代三 嗪钠盐的氯基分解, 不能进行有效的电子置换反应。第二次升温处理要求温度在 60T:〜 90Ό之间,具有亲水性取代基的二卤代三嗪钠盐的第二反应氯基将与含有 氨基纤维结构物中的 (-NH- )或含有醇羟基纤维结构物中的 (-0-)或含有羧基纤维 结构物中的(-C00- )进行共有结合反应。反应必要条件是温度在 601:〜 9CTC之间 处理 30〜90分钟。 然后进行冷水洗, 热水洗, 酸中和以及烘干以后, 纤维结构 物将会具有高效性、 耐久性的抗菌、 防臭及抗病毒功能。
本发明中所述 30°C〜9(TC环境下进行热处理, 包括升温热处理与连续热处理。 下面给出具体的实施例子, 揭示本发明的最隹实施方式, 旨在使本领域的普通技 术人员能够理解本发明涉及的技术方案和能够实施本发明。应当理解,本发明并 不受这些实施例约束。基于本发明启示, 任何显而易见的变换或替代, 也应当被 认为在本发明的保护范围之内。
实施例中浓度非特别注明, 均为重量%浓度。
实施例 1
染色水溶液水温控制在 25°C的条件下, 加入浓度各为 10%的 2, 6-二氯 -4-硫- R- 三嗪 Na盐 45毫升和 2, 6-二氯 -4-脲基- R-三嗪水溶液 45毫升中, 投入浓度为 1% (0. W. S) 的 3, 3 ' - 二甲氧基联苯胺 30毫升, 混合搅拌制成制剂; 将此制 剂 50毫升投入到玻璃容器当中, 投入 10g的碳酸钠, 15g的碳酸氢钠, 把 pH值 调到 9. 8, 然后注入含羟丙基酯甲壳糖 85%的溶液 10毫升, 混合搅拌。 在这个 溶液中投入 JIS规格白布 (标准白布) 80g, 含浸或浸渍 5分钟, 然后利用 20 分钟的时间将温度慢慢升至 60°C后, 再利用电热炉升温到 8(TC, 保持温度并搅 拌 30分钟。 结束后排水, 水洗 5分钟, 5(TC的水中进行 15分钟酸中和后排水, 再水洗。 然后, 利用传统的柔软剂进行烘干处理。
实施例 2
染色水溶液水温控制在 25Ό的条件下, 向 10%浓度的 2, 6-二氯 -4- ( 3-5-二磺 基苯胺基) -R-三嗪的水溶液 100毫升中投入浓度为 5% (0. W. S) 的 4, 4' - 二 氨基 - .3, 3 ' - 二氯二苯甲垸基 30毫升, 混合搅拌制成制剂; 将此制剂 15毫 升投入到玻璃容器当中, 投入 20g的碳酸钠, 把 pH值调到 10. 2, 然后注入含甘 油脂肪酸酯 80%的溶液 2毫升,混合搅拌。在这个溶液中投入 JIS规格白布(标 准白布) 55g, 含浸或浸渍 5分钟, 然后利用 20分钟的时间将温 慢慢升至 60 V后, 再利用电热炉升温到 80°C, 保持 80Ό温度搅拌 30分钟。 结束后排水, 水 洗 5分钟, 5CTC的水中进行 15分钟酸中和后再排水, 水洗。 然后, 利用传统的 柔软剂进行烘干处理。
实施例 3
染色水溶液水温控制在 25°C的条件下, 向 10%浓度的 2, 6-二氯 -4- (4-羧基苯 胺基) -R-三嗪的水溶液中投入浓度为 10% (0. W. S) 的氨基联苯- 2, 2 ' - 二磺 酸, 混合搅拌制成制剂; 将此制剂 10毫升投入到玻璃容器当中, 投入 10g的碳 酸钠, 15g的碳酸氢钠, 把 pH值调至 9. 7, 再注入含双十八垸基二甲基氯化铰 90%的溶液 15毫升, 混合搅拌。 在这个溶液中投入 JIS规格白布 (标准白布) 60g, 含浸或浸渍 5分钟, 然后利用 20分钟的时间将温度慢慢升至 60°C后, 再 用电热炉升温到 80Ό , 保持 80Ό温度搅拌 30分钟。 结束后排水, 水洗 5分钟, 50Ό的水中进行 15分钟酸中和后再排水, 水洗。 最后, 利用传统的柔软剂进行 烘干处理。
实施例 4
水温控制在 25°C的条件下, 向 10%浓度的 2, 6-二氯- 4-羟基 -R-三嗪 Na盐的水 溶液中投入浓度为 5% ( 0. W. S )的 2, 4 ' ― 二氨基苯磺酸钠,混合搅拌制成制剂; 将此制剂 8毫升投入到玻璃容器当中, 投入 10g的硫酸钠, 5g的碳酸氢钠, 10g 的氢氧化钠, 调 11值为 9. 2, 然后注入含双十垸基二甲基氯化铵 80%的溶液 5 毫升, 混合搅拌。 在这个溶液中投入 JIS规格白布 (标准白布) 60g, 含浸或浸 渍 5分钟, 然后利用 20分钟的时间将温度慢慢升至 60Ό后, 利用电热炉升温到 80V , 保持 80°C温度搅拌 30分钟。 结束后排水, 水洗 5分钟, 50°C的水中进行 15分钟酸中和后再排水, 水洗。 然后, 利用传统的柔软剂进行烘干处理。
实施例 5
在卷染机内注入 1000kg水、 2, 6-二氯- 4- ( 3-磺基苯胺基) - R-三嗪 10% ( 0. W. S ) 浓度的水溶液 20kg、 4, 4 ' - 二氨基二苯硫醚 10kg、 投入 15kg的碳酸钠, 10kg 的碳酸氢钠, 把 pH值调和到 10. 9后, 注入含亥巴油乳剂 85 %的溶液 5升, 常 温搅拌均匀, 放入 40kg的 100%府绸棉, 充分弄湿后运转 5分钟。 之后, 以 1. 5 °C/分钟的速度用 20分钟时间把水溶液温度升温到 60°C后, 用 15分钟时间再升 温到 80°C, 维持水温搅拌运转 30分钟后排水, 注水, 在 40°C水温中进行 10分 钟的酸中和处理, 排水后再清洗干净, 利用传统的柔软剂进行烘千处理。
实施例 6
在卷染机内注入 1000kg水、 2, 6-二氯 -4-( β -羧基乙基氨基) -R-三嗪 10%(0. W. S ) 浓度的水溶液 25kg、 5, 5 ' - 亚甲基二氨茴酸 12kg、 投入 10kg的硫酸钠, 5kg 的碳酸钠, 10kg的碳酸氢钠, 把 pH值调到 11. 2后, 常温搅拌。 注入含 PHMB多 水氯硼钙石 85 %的溶液 5升,放入 40kg的 100%府绸棉,充分弄湿后运转 5分钟。 以 1. 5°C/分钟的速度用 20分钟时间把水溶液温度升温到 60Ό后, 用 15分钟时 间再升温到 80Ό , 在 80Ό的水温中保温运转 30分钟后排水, 注水, 在 40Ό水 温中进行 10分钟的酸中和处理, 排水后再度清洗干净, 利用传统的柔软剂进行 烘干处理。
实施例 7
在液流染色机内注入 500kg水、 2, 6-二氯- 4-脲基 -R-三嗪 10% (0. W. S )浓度的 水溶液 12kg、 3, 3 ' - 二氨基二苯砜 6kg、 投入 10kg的氢氧化钠, 3kg的碳酸 钠, pH值调到 11. 7, 常温搅拌, 之后, 注入含十二垸基三甲基氯化铵 90%的 溶液 3升,放入 20kg的 100%棉布, 充分弄湿后运转 5分钟。 之后, 以 1. 5Ό/分 钟的速度用 20分钟时间把水溶液温度升温到 6(TC后, 用 15分钟时间再升温到 80Ό , 在 80Ό的水温中机器保温运转 30分钟后排水, 注水, 在 40Ό水温中进行 10 分钟的酸中和处理, 排水后再度清洗干净, 最后, 利用传统的柔软剂进行烘 千处理。
实施例 8
在液流染色机内注入 860kg水、 2, 6-二氯- 4- (4-羧基苯氧基) -R-三嗪 10%(0. W. S) 浓度的水溶液 17kg、 4, 6 -苯二胺 - 1, 3 -二磺酸 9kg、 投入 4. 5kg的碳酸钠, 9kg的碳酸氢钠, 把 pH值调至 9. 7, 常温搅拌, 之后, 注入含聚环氧乙垸氯硼钙 石 90%的溶液 5升,放入 20kg的 100%羊毛面料, 充分弄湿后, 运转 5分钟。 以 1. 5°C/分钟的速度用 20分钟时间把水溶液温度升温到 60°C后, 用 15分钟时间 再升温到 80°C, 在 80'C的水温中保温运转 30分钟后排水, 注水, 在 40°C水温 中进行 10分钟的酸中和处理, 排水后再度清洗干净, 最后, 利用传统的柔软剂 进行烘干处理。
实施例 9
在束状染色机内注入 1500kg水、 2, 6-二氯- 4-羟基- R-三嗪 Mg盐 10% (0. W. S) 浓度的水溶液 15kg和 2, 6-二氯- 4- ( β -羧基乙基氨基) - R-三嗪 10% (0. W. S) 浓度的水溶液 10kg、 3, 4 - 二氨基苯甲酸 18kg、 投入 30kg的碳酸钠, 把 pH 值调到 10. 9, 常温搅拌, 注入含 N, N-二甲基 -N- (二氯氟甲硫基) - N, -苯基磺 酰胺 90%的溶液 10升,放入 35kg的 100%羊毛面料,充分弄湿后运转 5分钟。之 后, 以 1. 5Ό/分钟的速度用 20分钟时间把水溶液温度升温到 60°C后, 用 15分 钟时间再升温到 8(TC, 在 8(TC的水温中机器保温运转 30分钟后排水, 注水后, 在 40°C水温中进行 10分钟的酸中和处理, 排水后再度清洗干净, 最后, 利用传 统的柔软剂进行烘干处理。
由本发明的方法加工的棉布, 委托日本京都府立医科大学利用 JIS L-1902菌液 吸尽法, 对禽流感病毒进行不活性化试验。经过处理的棉布, 对禽流感病毒的平 均抗病毒率为 99. 87%。 经过日本京都织物机械金属中心利用 LIS L 0217 103法, 对同样品水洗 50次之后, 该大学进行同样的试验, 对禽流感病毒的平均抗病毒 率为 99. 92%, 证明了本发明加工方法具有持久的效果。 试验结果见表 1。
表 1 测试单位: 京都府立大学 PFU/mL 病毒减少率 未加工标准白布 1. 61 X 105
未加工标准白布 1. 78 X 105
未加工标准白布 1. 63 X 105
平均 1. 67 X 105
加工未水洗白布 350 99. 79% 加工未水洗白布 150 99. 91% 加工未水洗白布 150 99. 91% 平均 217 99. 87% 加工水洗 50 次白布
200 99. 88%
(水洗方法: LIS L 0217 103法)
加工水洗 50 次白布
100未満 99. 94%以上
(水洗方法: LIS L 0217 103法)
加工水洗 50 次白布
100 99. 94%
(水洗方法: LIS L 0217 103法)
平均 99. 92%以上
※试验材料: 棉布 (JIS标准白布)
※病毒: 禽流感病毒 A/Duck/Hong Kong/342/78 (H5N2) 10 X 105 ※试验方法: JIS L-1902
由日本化学纤维协会生物试验中心利用 JIS L- 1902菌液吸尽法, 对加工过的棉 布进行 MRSA (Methici 11 in-Resistant Staphylococcus Aureus ) LLD 1677抗菌 试验。证明了该加工方法对该菌具有杀菌效果。经过日本京都织物机械金属中心 利用 LIS L 0217 103法,对同制品水洗 50次以后的棉布, 由该协会进行了同样 的试验, 再次证明了本发明加工方法具有持久的效果。 试验结果见表 2。
试验单位: 日本财团法人化学纤维检査协会生物试验中心
Figure imgf000012_0001
加工水洗 50 次白布
4. 4 <1. 3 〉5. 6 >3. 1
(水洗: LIS L 0217 103法)
未加工标准白布 4. 4 6. 9 - 一 抗菌防臭标准: 静菌活性值 2. 2以上 防菌加工: 杀菌活性值 0. 0以上
※试验材料: 棉布 (JIS标准白布)
※病菌: MRSA (Methici 11 in-Resistant Staphylococcus Aureus) LLD 1677 ※试验方法: JIS L-1902
注: 使用界面活性剂 TWeen80
由日本化学纤维协会生物试验中心利用 JIS L- 1902菌液吸尽法, 针对加工过的 羊毛面料进行金黄色葡萄球菌抗菌测试。 证明了该加工方法对该菌具有抗菌效 果。 试验结果见表 3。
表 3 试验单位: 日本财团法人化学纤维检査协会生物试验中心
Figure imgf000013_0001
抗菌防臭标准: 静菌活性值 2. 2以上
※试验材料: 羊毛面料
※病菌: 金黄色葡萄球菌 ATCC 6538P
※试验方法: JIS L-1902
注: 使用界面活性剂 Tween80
通过以上表 1〜表 3所示, 证明了本发明加工方法处理的纤维制品具有高效、 持 久的抗菌, 防臭, 抗病毒效果。

Claims

权利要求:
1.一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,包括染色水溶液初始温 度低于 30Ό时投入纤维结构物含浸或浸渍 5〜10分钟, 其特征在于: 染色水溶 液中具有亲水性取代基的二卤代三嗪钠盐、芳香胺化合物以及具有亲水性的有机 类的抗菌、 防臭及杀毒剂共存, 调节 pH值为 8. 0〜13. 0, 并利用含浸法或浸渍 法缓慢升温在 30°C〜9(TC度环境下进行热处理。
2.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于: 所述具有亲水性取代基的二卤代三嗪类钠盐为 2, 6-二卤代 - 4-Y-1 ,
3. 5-三嗪衍生物, 其结构式如通式(1)所示:
Y
I
N N
通式 (1 ) 中, X指的是氯, 氟以及溴类中选出来的卤素基, Y指的是由磺基、 羧 基、氢氧根以及硫醇基类中至少选出一种基被芳氨基、芳氧基、芳巯基、垸氨基、 垸氧基、 垸硫基、 三嗪氨基、 三嗪氧基、 三嗪硫基所取代。
3.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于: 所述芳香胺化合物为: 4, 4 ' -二氨基二苯硫醚、 4, 4 ' - 二氨基- 3, 3 ' - 二氯二苯甲烷基、氨基联苯 _ 2, 2 ' -二磺酸、 2, 4 ' -二氨基苯磺酸钠、 3, 3 ' -二甲氧基联苯胺、 5, 5 ' -亚甲基二氨茴酸、 3, 3 ' -二氨基二苯砜、 4, 6 - 苯二胺 - 1, 3 -二磺酸、 3, 4 - 二氨基苯甲酸、 1, 4-二氨基蒽醌- 2, 3 -二磺 酸中的一种。
4.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于:所述具有亲水性的有机类的抗菌、防臭及杀毒剂中至少含有一个以上 的亲水性 NH2基、 0H基、 SH基、 或 C00H基。
5.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于:所述具有亲水性的有机类的抗菌、防臭及杀毒剂为:羟丙基酯甲壳糖、 甘油脂肪酸酯、双十八烷基二甲基氯化铵、双十烷基二甲基氯化铵、亥巴油乳剂、
PHMB 多水氯硼钙石和氧化亚铅的配合物、 十二烷基三甲基氯化铵、 聚环氧乙院 氯硼钙石、 N, N-二甲基 -N- (二氯氟甲硫基) - N, -苯基磺酰胺、 双辛烷基二甲 基氯化铵、 二氯甲烷中的一种。
6.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于: 所述纤维结构物具有末端基为 H的亲水性的 NH2基、 0H基、 SH基、 或 C00H基。
7.根据权利要求 1所述一种赋予纤维结构物抗菌、防臭及抗病毒功能的方法,其 特征在于: 所述纤维结构物为天然真丝、毛、棉、麻; 以及再生纤维人造丝、涤、 尼龙或皮革、 羽毛。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004292975A (ja) * 2003-03-26 2004-10-21 Toray Ind Inc ナイロン繊維からなる繊維構造物の改質製法
JP2004346471A (ja) * 2003-05-20 2004-12-09 Yoshiki Hagiwara 真珠粉末を用いた天然繊維材料の改質加工法
CN1942624A (zh) * 2004-03-03 2007-04-04 住友商事株式会社 纤维结构物的疏水化方法
CN101008151A (zh) * 2006-09-11 2007-08-01 李民旭 对有机纤维结构物性能的改良和赋予疏水性功能的方法
JP2008063708A (ja) * 2006-09-09 2008-03-21 Kanehisa:Kk 有機繊維構造物の改質.疎水化製造方法

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JP2004292975A (ja) * 2003-03-26 2004-10-21 Toray Ind Inc ナイロン繊維からなる繊維構造物の改質製法
JP2004346471A (ja) * 2003-05-20 2004-12-09 Yoshiki Hagiwara 真珠粉末を用いた天然繊維材料の改質加工法
CN1942624A (zh) * 2004-03-03 2007-04-04 住友商事株式会社 纤维结构物的疏水化方法
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