WO2020073783A1 - 一种抗菌织物材料及其制备方法 - Google Patents

一种抗菌织物材料及其制备方法 Download PDF

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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
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antibacterial
guanidine
reaction
fabric material
preparation
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PCT/CN2019/106763
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English (en)
French (fr)
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刘及响
赵云瑞
李郁聪
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桂林新先立抗菌材料有限公司
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    • 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.

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  • 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

本发明提供了一种抗菌织物材料及其制备方法，其中的抗菌母料由多元醇与胍盐聚合而成，具有以下结构：(I) 抗菌母料制备方法中使用无毒无刺激的多元醇为原料对环境和人体友好。

Description

一种抗菌织物材料及其制备方法 一技术领域
本申请属于纺织品材料领域和环保领域，具体的，本申请提供了一种抗菌织物材料及其制备方法，其中的抗菌母料使用无毒/无刺激的多元醇与胍盐聚合而成。
二背景技术
用于服装、包袋等用途的化纤纺织品主要包括尼龙、聚酯、聚丙烯等种类，这些抗菌织物由于自身的微孔结构、穿着者的体温、人体散发的湿气以及皮肤的代谢物等因素，为微生物提供了合适的生长环境，使其成为了适合细菌和霉菌等微生物滋生和繁殖的温床。化纤纺织品上滋生的这些细菌,不仅会使织物变色、发霉、脆化降解，而且对人体皮肤产生刺激并诱发各种皮肤疾病，影响人体健康。向抗菌织物中添加抗菌剂制备抗菌织物，成为解决这一问题的主要途径。
可用于抗菌织物中的抗菌剂可分为无机类、有机类和天然类。天然抗菌剂的价格、稳定性上存在较多的问题，无法成为纺织工业中的主流抗菌添加剂。无机抗菌剂，如常用的纳米银材料或锌离子材料制备工艺复杂、产品质量不稳定(粒度大、团聚等)、抗菌种类也有限(特别是抗霉菌效果不佳)。有机抗菌剂主要包括季铵盐类、醚类、苯酚类等，其问题主要在于抗菌种类受限较多且稳定性，特别是对水、热、洗涤剂等化学产品的稳定性不足(可能源于有机抗菌剂本身的化学变化或者抗菌产品上新表面层的形成隔绝了抗菌物质与外界菌体的接触)，这些问题在用于经常要经受洗涤的衣物材料时更为显著。
发明人先前将多元胺与胍盐聚合，获得了一种抗菌母料并取得了中国专利CN1111556C，随后的应用中，该母料被实际用于塑料、纤维、涂料等方面，取得了良好的实际效果。但该母料虽然抗霉菌效果良好，但与大多数有机抗菌剂一样存在耐水耐洗涤性能不足的问题(胍结构的水溶性使这一问题更为显著)。含胍结构的聚合物抗菌剂存在进一步改进的需求。而且包括CN1111556C在内的现有此类抗菌母料多采用有毒/刺激性的原料如多元胺，产生的污水废料对环保不利且织物产品上可能的残留会对人体皮肤有刺激。含胍结构的聚合物抗菌剂存在进一步改进的需求。
三发明内容
针对上述问题，发明人进一步改进了CN1111556C的含胍结构的聚合物抗菌剂，使用多元醇与胍盐聚合制备了新型抗菌聚合物，该聚合物在保持类似CN1111556C抗菌聚合物抗菌 性能的前提下，实现了耐热、耐水、耐洗涤剂能力的显著提高，使得其更适合用于经常接受洗涤的衣物包袋纤维材料的制备；而且采用无毒/无刺激的多元醇作为原料，对环境比多元胺更为友好，并且避免了织物对人体刺激的潜在可能性。
一方面，本申请提供了一种抗菌织物材料，其中包括抗菌聚合物，所述抗菌聚合物由多元醇或多元胺与胍盐聚合而成。
进一步地，该抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
Figure PCTCN2019106763-appb-000001
其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X。
进一步地，该抗菌聚合物中，X选自丙烯酸酯基、甲基丙烯酸酯基、丁烯酸酯基、十一碳烯酯基、丙烯酸乙酯基、丙烯酸丙酯基或甲基丙烯酸羟基丙酯基。
进一步地，该抗菌聚合物按以下方法制备：将多元醇与胍盐以摩尔比1：0.8-1.8的比例混合。加入反应器中，氮气保护下，调pH至酸性，加热至120-180℃，反应1-4小时，而后再加入多元醇和胍盐重量5％-25％的含活性不饱和双键的C3-C20化合物，进行酯化或开环缩合反应，10-120分钟后，结束反应。
进一步地，多元醇与胍盐的摩尔比为1：1-1.5。
进一步地，多元醇选自乙二醇、丙二醇、丁二醇、戊二醇、1，6-己二醇、1，10-癸二醇；胍盐选自碳酸胍、盐酸胍、硝酸胍、硫酸胍、磷酸胍、乙酸胍；含活性不饱和双键的C3-C20化合物选自丙烯酸、甲基丙烯酸、丙烯酸环氧乙酯、丙烯酸环氧丙酯、丙烯酸环氧丁酯、甲基丙烯酸环氧丙酯、甲基丙烯酸环氧乙酯、甲基丙烯酸环氧丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、甲基丙烯酸环氧丙酯、甲基丙烯酸-2-羟基丙酯、马来酸酐、富马酸酯、衣康酸。
进一步地，制备方法具体包括：
取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。
进一步地，制备方法具体包括：
取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。
四具体实施方式
实施例1本申请抗菌母料的制备
1.1取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。造粒。
产品分子量约8300，热分解温度约340℃，红外图谱显示应有的特征吸收峰。
1.2取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，以盐酸调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。造粒。
产品分子量约10600，热分解温度约300℃，红外图谱显示应有的特征吸收峰。
实施例2本申请织物材料的制备
织物材料具体制备由合作纺织企业完成；CN1111556C的抗菌母料按照该公开文本中的实施例1制备；本申请的抗菌母料按照实施例1(1.1)的方法制备；聚丙烯纺丝料颗粒为购自上海桥微化工科技有限公司的常规种类；合作企业所用的纺丝机和编织机由无锡华兰纺织机械有限公司生产调试。
取聚丙烯纺丝料颗粒100重量份，与可选的4重量份本申请抗菌母料/CN1111556C抗菌母料充分混合，使用小试级别纺丝机生产约150旦尼尔/28丝的细丝，随后编制为织物材料。
材料1：加入本申请抗菌母料；
材料2：加入CN1111556C抗菌母料；
材料3：不加入抗菌母料；
为检测本申请抗菌织物材料的耐热水和耐洗涤浸泡性能，对材料1和2进行进一步处理
材料1-1：材料1经70℃热水浸泡48小时，干燥；
材料1-2：材料1塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，预洗浸泡12小时后，以普通程序30℃洗涤40次(每次约1小时)，漂洗干净，干燥；
材料2-1：材料2经70℃热水浸泡48小时，干燥；
材料2-2：材料2塑料片在滚筒式洗衣机中加入说明书推荐量的洗衣液(蓝月亮，无香型)，预洗浸泡12小时后，以普通程序30℃洗涤40次(每次约1小时)，漂洗干净，干燥；
处理后的材料均无明显破损。
实施例3织物材料抗菌性能检测
抗菌性能检测由中国科学院理化所抗菌材料检测中心进行，抗细菌和白色念珠菌性能参 照GB/T 20944.3-2008震荡法:将试样置于烧瓶中、加入接种菌液、震荡，吸取瓶中液体，置于平板培养48小时(白色念珠菌72小时)，记录菌落数(cfu/ml)计算抑菌率。抗霉菌性能参照AATCC30中琼脂平板法：将霉菌接种液均匀滴加在圆片试样上，培养14日，观察霉菌覆盖率。
测试对象包括金黄色葡萄球菌(Staphylococcus aureus)ATCC 6538、大肠埃希氏菌(Escherichia coli)ATCC 25922、白色念珠菌(Canidia Albicans)ATCC 10231以及真菌黑曲霉(Aspergillus niger)ATCC 6275。
表1织物材料的抗细菌/白色念珠菌性能
Figure PCTCN2019106763-appb-000002
*参照标准，90％以下即不能称为有抗菌作用。
表2.织物材料的抗霉菌性能
样品编号 黑曲霉长霉生长情况
材料1 无生长
材料2 无生长
材料3 宏观生长
材料1-1 无生长
材料2-1 微观生长
材料1-2 无生长
材料2-2 宏观生长
*三种生长情况标准：无生长：不可见、微观生长：显微镜下可见、宏观生长：肉眼可见。
实施例2、3的数据显示，本申请抗菌母料的抗菌性能与CN1111556C抗菌母料相似，但制备成织物材料时，耐热水耐洗涤能力明显高于CN1111556C抗菌母料，在常规洗涤剂长时间浸泡后，本申请抗菌母料制备的织物材料对抗细菌霉菌性能影响轻微甚至没有影响，而CN1111556C抗菌母料制备的织物材料几乎丧失大部分抗菌性能，特别是抗霉菌和白色念珠菌性能几乎丧失殆尽。
另外的实验表明，含实施例1(1.2)抗菌聚合物的织物材料机械和抗菌性能与含实施例1(1.1)的近似，同时制成的无织物也具有类似的耐受热水浸泡和洗涤能力(为节约时间和费用未委托进行完整检测)。
本申请的织物材料的上述特点使得其更适合制备衣物、包袋等日用品，这些用品在使用时不可避免要经常经历洗涤，本申请的织物材料在多次洗涤后仍然能基本保持抗菌能力。
上述实施例中的织物材料配方和制备工艺仅是为了举例列出，其余织物母料如尼龙，聚酯等，以及其他辅料与本申请抗菌母料配合的技术方案的抗菌效果可以从实施例2、3合理预期，并且这些技术方案也在本申请公开和要求保护的范围内。

Claims (2)

  1. 一种抗菌织物材料，其中包括抗菌聚合物，其中的抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106763-appb-100001
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X，所述抗菌聚合物按照以下方法制备：取乙二醇124g，硝酸胍260g，加入反应釜中，混合均匀，氮气保护下，调pH为5，加热至120℃，反应3h，再加入丙烯酸30g，进行酯化反应1h，结束反应。
  2. 一种抗菌织物材料，其中包括抗菌聚合物，其中的抗菌聚合物由多元醇与胍盐聚合而成，具有以下结构：
    Figure PCTCN2019106763-appb-100002
    其中n＝5-10，m＝50-150；Y -为选自Cl -、NO 3 -、HCO 3 -、CH 3COO -、HSO 4 -或H 2PO 4 -阴离子；X为含1-5个活性不饱和双键的C5-C20酯基或醚基；Z为H或X，所述抗菌聚合物按照以下方法制备：取丙二醇152g，碳酸胍254g，加入反应釜中，混合均匀，氮气保护下，调pH为4，加热至130℃，反应2.5h，再加入甲基丙烯酸25g，进行酯化反应1.5h，结束反应。
PCT/CN2019/106763 2018-10-10 2019-09-19 一种抗菌织物材料及其制备方法 WO2020073783A1 (zh)

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