WO2020073783A1 - Matériau de tissu antimicrobien et son procédé de préparation - Google Patents

Matériau de tissu antimicrobien et son procédé de préparation Download PDF

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Publication number
WO2020073783A1
WO2020073783A1 PCT/CN2019/106763 CN2019106763W WO2020073783A1 WO 2020073783 A1 WO2020073783 A1 WO 2020073783A1 CN 2019106763 W CN2019106763 W CN 2019106763W WO 2020073783 A1 WO2020073783 A1 WO 2020073783A1
Authority
WO
WIPO (PCT)
Prior art keywords
antibacterial
guanidine
reaction
fabric material
preparation
Prior art date
Application number
PCT/CN2019/106763
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English (en)
Chinese (zh)
Inventor
刘及响
赵云瑞
李郁聪
Original Assignee
桂林新先立抗菌材料有限公司
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Application filed by 桂林新先立抗菌材料有限公司 filed Critical 桂林新先立抗菌材料有限公司
Publication of WO2020073783A1 publication Critical patent/WO2020073783A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms

Definitions

  • the present application belongs to the field of textile materials and the field of environmental protection. Specifically, the present application provides an antibacterial fabric material and a preparation method thereof, wherein the antibacterial masterbatch is formed by polymerizing a non-toxic / non-irritating polyol and a guanidine salt.
  • Chemical fiber textiles used for clothing, bags, etc. mainly include nylon, polyester, polypropylene and other types. These antibacterial fabrics are due to their microporous structure, wearer's body temperature, human body moisture, and skin metabolites. , Provides a suitable growth environment for microorganisms, making it a suitable breeding ground for bacteria and mold and other microorganisms. These bacteria that grow on chemical fiber textiles will not only discolor, mold, embrittle and degrade the fabric, but also stimulate human skin and induce various skin diseases, affecting human health. Adding antibacterial agent to antibacterial fabric to prepare antibacterial fabric has become the main way to solve this problem.
  • Antibacterial agents that can be used in antibacterial fabrics can be divided into inorganic, organic, and natural types. There are many problems in the price and stability of natural antibacterial agents, and they cannot become mainstream antibacterial additives in the textile industry.
  • Inorganic antibacterial agents such as commonly used nano silver materials or zinc ion materials, have complex preparation processes, unstable product quality (large particle size, reunion, etc.), and limited types of antibacterial (especially poor anti-fungal effects).
  • Organic antibacterial agents mainly include quaternary ammonium salts, ethers, phenols, etc.
  • the main problem is that the types of antibacterial are more limited and stable, especially for water, heat, detergents and other chemical products that are not stable enough (possible source (The chemical change of the organic antibacterial agent itself or the formation of a new surface layer on the antibacterial product isolates the contact between the antibacterial substance and the external bacterial cells.) These problems are more significant when used in laundry materials that are often subjected to washing.
  • the inventors previously polymerized polyamines and guanidine salts to obtain an antibacterial masterbatch and obtained the Chinese patent CN1111556C.
  • the masterbatch was actually used in plastics, fibers, coatings, etc., and achieved good practice. effect.
  • the masterbatch has a good anti-fungal effect, it has the problem of insufficient water and washing resistance like most organic antibacterial agents (the water solubility of the guanidine structure makes this problem more pronounced).
  • the inventors further improved the polymer antibacterial agent containing a guanidine structure of CN1111556C, and prepared a new type of antibacterial polymer by polymerizing a polyhydric alcohol and a guanidine salt.
  • the polymer maintained the antibacterial performance similar to that of the CN1111556C antibacterial polymer. Achieved a significant increase in heat resistance, water resistance, and detergent resistance, making it more suitable for the preparation of fiber materials for clothing bags that often receive washing; and using non-toxic / non-irritating polyols as raw materials, which is more diverse than the environment Amine is more friendly and avoids the potential for fabric irritation to the human body.
  • the present application provides an antibacterial fabric material, which includes an antibacterial polymer, which is formed by polymerizing a polyhydric alcohol or a polyamine and a guanidinium salt.
  • the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:
  • X is selected from acrylate group, methacrylate group, crotonate group, undecylenate group, ethyl acrylate group, propyl acrylate group or hydroxypropyl methacrylate group Ester group.
  • the antibacterial polymer is prepared by the following method: the polyol and the guanidine salt are mixed in a molar ratio of 1: 0.8-1.8. Add to the reactor, adjust the pH to acidic under the protection of nitrogen, heat to 120-180 °C, react for 1-4 hours, and then add 5% -25% by weight of polyol and guanidine salt containing active unsaturated double bond C3- The C20 compound undergoes esterification or ring-opening condensation reaction, and the reaction is terminated after 10 to 120 minutes.
  • the molar ratio of polyol to guanidine salt is 1: 1 to 1.5.
  • the polyhydric alcohol is selected from ethylene glycol, propylene glycol, butylene glycol, pentanediol, 1,6-hexanediol, 1,10-decanediol
  • the guanidine salt is selected from guanidine carbonate, guanidine hydrochloride, guanidine nitrate, Guanidine sulfate, guanidine phosphate, guanidine acetate
  • C3-C20 compounds containing active unsaturated double bonds are selected from acrylic acid, methacrylic acid, epoxyethyl acrylate, glycidyl acrylate, epoxybutyl acrylate, methacrylic acid ring Oxypropyl ester, epoxy ethyl methacrylate, epoxy butyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid- 2-hydroxy
  • preparation method specifically includes:
  • preparation method specifically includes:
  • the molecular weight of the product is about 8300, the thermal decomposition temperature is about 340 °C, and the infrared spectrum shows the characteristic absorption peak.
  • the molecular weight of the product is about 10600, the thermal decomposition temperature is about 300 °C, and the infrared spectrum shows the characteristic absorption peak.
  • Material 1-1 Material 1 is soaked in hot water at 70 ° C for 48 hours and dried;
  • Material 1-2 Material 1 Plastic tablets are added to the drum-type washing machine with the recommended amount of washing liquid (blue moon, unscented type), pre-washed for 12 hours, and washed 40 times (approximately 1 each time) Hours), rinse and dry;
  • Material 2-1 Material 2 is soaked in hot water at 70 ° C for 48 hours and dried;
  • Material 2-2 Material 2 plastic sheet is added to the drum-type washing machine with the recommended amount of laundry liquid (blue moon, no fragrance), after pre-washing and soaking for 12 hours, it is washed 40 times (approximately 1 each time) at 30 °C Hours), rinse and dry;
  • the treated materials were not significantly damaged.
  • the antibacterial performance test is carried out by the Antibacterial Material Testing Center of the Institute of Physics and Chemistry, Chinese Academy of Sciences.
  • the antibacterial and Candida albicans performance is according to GB / T 20944.3-2008 Shaking method: Place the sample in the flask, add the inoculated bacterial liquid, shake, and absorb the liquid in the bottle , Place on plate for 48 hours (72 hours for Candida albicans), record the number of colonies (cfu / ml) to calculate the inhibition rate.
  • the anti-fungal performance refers to the agar plate method in AATCC30: the mold inoculum was evenly added to the disc sample, and cultured for 14 days to observe the mold coverage.
  • Test subjects include Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231 and the fungus Aspergillus niger ATCC 6275.
  • the data of Examples 2 and 3 show that the antibacterial properties of the antibacterial masterbatch of this application are similar to the CN1111556C antibacterial masterbatch, but when prepared as a fabric material, the resistance to hot water and washing is significantly higher than that of the CN1111556C antibacterial masterbatch. After time immersion, the fabric material prepared by the antibacterial masterbatch of this application has little or no effect on the resistance to bacteria and fungi, while the fabric material prepared by the CN1111556C antibacterial masterbatch has almost lost most of its antibacterial properties, especially the resistance to mold and Candida albicans Exhausted.
  • the above-mentioned characteristics of the fabric material of the present application make it more suitable for the preparation of daily necessities such as clothes and bags. These articles are inevitably subjected to frequent washing.
  • the fabric material of the present application can still basically maintain antibacterial ability after multiple washings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un matériau textile antimicrobien et son procédé de préparation. Un mélange maître antimicrobien de celui-ci est formé par polymérisation d'un polyol et d'un sel de guanadine, et présente la structure : (I). L'utilisation d'un polyol non toxique et non irritant en tant que matière première dans le procédé de préparation du mélange maître antimicrobien est respectueuse de l'environnement et du corps humain.
PCT/CN2019/106763 2018-10-10 2019-09-19 Matériau de tissu antimicrobien et son procédé de préparation WO2020073783A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811179910.5 2018-10-10
CN201811179910.5A CN109535418B (zh) 2018-10-10 2018-10-10 一种抗菌织物材料及其制备方法

Publications (1)

Publication Number Publication Date
WO2020073783A1 true WO2020073783A1 (fr) 2020-04-16

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CN (1) CN109535418B (fr)
WO (1) WO2020073783A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467698B (zh) 2018-10-10 2019-08-30 桂林新先立抗菌材料有限公司 一种抗菌聚合物及其制备方法
CN109535418B (zh) * 2018-10-10 2019-08-30 桂林新先立抗菌材料有限公司 一种抗菌织物材料及其制备方法
CN110777442A (zh) * 2019-11-06 2020-02-11 吉林师范大学 衣康酸胍基苯乙烯共聚消毒纤维制备方法

Citations (9)

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Publication number Priority date Publication date Assignee Title
CN1350022A (zh) * 2000-10-19 2002-05-22 上海塑杰科技有限公司 一种多元胺与胍盐聚合物及其制备方法
CN1569923A (zh) * 2003-07-23 2005-01-26 上海塑杰科技有限公司 一种多元胺与胍盐聚合物及其在抗菌聚酯和聚酰胺材料中的应用
US20060127457A1 (en) * 2004-12-10 2006-06-15 Gilbert Buchalter Fabrics impregnated with antimicrobial agents
CN101173041A (zh) * 2007-10-19 2008-05-07 华南理工大学 高分子量胍盐和多元胺抗菌型聚合物及其制备方法与应用
CN101250263A (zh) * 2007-11-28 2008-08-27 广州科仁机电有限公司 一种多元胺与胍盐预聚物、聚合物及其制备方法和应用
WO2011057611A1 (fr) * 2009-11-12 2011-05-19 Philipps-Universität Marburg Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomère
CN106075577A (zh) * 2016-07-21 2016-11-09 南京工业大学 基于有机胍盐和聚乙二醇的抗菌涂层
CN107254045A (zh) * 2017-05-26 2017-10-17 天津大学 一种胍类聚合物杀菌剂的制备方法
CN109535418A (zh) * 2018-10-10 2019-03-29 桂林新先立抗菌材料有限公司 一种抗菌织物材料及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1350022A (zh) * 2000-10-19 2002-05-22 上海塑杰科技有限公司 一种多元胺与胍盐聚合物及其制备方法
CN1569923A (zh) * 2003-07-23 2005-01-26 上海塑杰科技有限公司 一种多元胺与胍盐聚合物及其在抗菌聚酯和聚酰胺材料中的应用
US20060127457A1 (en) * 2004-12-10 2006-06-15 Gilbert Buchalter Fabrics impregnated with antimicrobial agents
CN101173041A (zh) * 2007-10-19 2008-05-07 华南理工大学 高分子量胍盐和多元胺抗菌型聚合物及其制备方法与应用
CN101250263A (zh) * 2007-11-28 2008-08-27 广州科仁机电有限公司 一种多元胺与胍盐预聚物、聚合物及其制备方法和应用
WO2011057611A1 (fr) * 2009-11-12 2011-05-19 Philipps-Universität Marburg Principes actifs polymères ou oligomères ayant une action biocide, procédé pour les préparer et composition comprenant un principe actif polymère ou oligomère
CN106075577A (zh) * 2016-07-21 2016-11-09 南京工业大学 基于有机胍盐和聚乙二醇的抗菌涂层
CN107254045A (zh) * 2017-05-26 2017-10-17 天津大学 一种胍类聚合物杀菌剂的制备方法
CN109535418A (zh) * 2018-10-10 2019-03-29 桂林新先立抗菌材料有限公司 一种抗菌织物材料及其制备方法

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CN109535418B (zh) 2019-08-30
CN109535418A (zh) 2019-03-29

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