WO2020073783A1 - Antimicrobial fabric material and preparation method therefor - Google Patents

Abstract

Provided in the present invention is an antimicrobial fabric material and a preparation method therefor. An antimicrobial master batch thereof is formed by means of polymerization of a polyol and a guanadine salt, and has the structure: (I). The use of a non-toxic and non-irritating polyol as a raw material in the preparation method for the antimicrobial master batch is friendly to the environment and to the human body.

Description

Antibacterial fabric material and preparation method thereof One technical field

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.

Two background technologies

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. In subsequent applications, the masterbatch was actually used in plastics, fibers, coatings, etc., and achieved good practice. effect. However, although 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). There is a need for further improvement of polymer antibacterial agents containing a guanidine structure. Moreover, existing antibacterial masterbatches, including CN1111556C, mostly use toxic / irritating raw materials such as polyamines, and the waste water generated is not environmentally friendly and the possible residues on textile products can irritate human skin. There is a need for further improvement of polymer antibacterial agents containing a guanidine structure.

Three summary

In response to the above problems, 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.

In one aspect, 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.

Further, the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 reactive unsaturated double bond C5-C20 ester or ether groups; Z is H or X.

Further, in the antibacterial polymer, X is selected from acrylate group, methacrylate group, crotonate group, undecylenate group, ethyl acrylate group, propyl acrylate group or hydroxypropyl methacrylate group Ester group.

Further, 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 ℃, 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.

Further, the molar ratio of polyol to guanidine salt is 1: 1 to 1.5.

Further, 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-hydroxypropyl ester, glycidyl methacrylate, 2-hydroxypropyl methacrylate, maleic anhydride, fumarate, itaconic acid.

Further, the preparation method specifically includes:

Take 124g of ethylene glycol and 260g of guanidine nitrate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 5 with hydrochloric acid, heat to 120 ° C, react for 3h, then add 30g of acrylic acid, perform esterification reaction for 1h, and end the reaction .

Further, the preparation method specifically includes:

Take 152g of propylene glycol and 254g of guanidine carbonate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 4 with hydrochloric acid, heat to 130 ° C, react for 2.5h, then add 25g of methacrylic acid, and perform the esterification reaction for 1.5h. End the reaction.

Four specific embodiments

Example 1 Preparation of antibacterial masterbatch of this application

1.1 Take 124g of ethylene glycol and 260g of guanidine nitrate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 5 with hydrochloric acid, heat to 120 ° C, react for 3h, then add 30g of acrylic acid, and perform the esterification reaction for 1h. reaction. Granulation.

The molecular weight of the product is about 8300, the thermal decomposition temperature is about 340 ℃, and the infrared spectrum shows the characteristic absorption peak.

1.2 Take 152g of propylene glycol and 254g of guanidine carbonate, add to the reaction kettle, mix evenly, under the protection of nitrogen, adjust the pH to 4 with hydrochloric acid, heat to 130 ° C, react for 2.5h, then add 25g of methacrylic acid, and perform the esterification reaction for 1.5h To end the reaction. Granulation.

The molecular weight of the product is about 10600, the thermal decomposition temperature is about 300 ℃, and the infrared spectrum shows the characteristic absorption peak.

Example 2 Preparation of the fabric material of the present application

The specific preparation of fabric materials is completed by the cooperative textile enterprise; the antibacterial masterbatch of CN1111556C is prepared according to Example 1 in this publication; the antibacterial masterbatch of this application is prepared according to the method of Example 1 (1.1); the polypropylene spinning material particles are The conventional type purchased from Shanghai Qiaowei Chemical Technology Co., Ltd .; the spinning machine and knitting machine used by the cooperative enterprise are produced and commissioned by Wuxi Hualan Textile Machinery Co., Ltd.

Take 100 parts by weight of polypropylene spinning material particles and mix it with the optional 4 parts by weight of antibacterial masterbatch / CN1111556C antibacterial masterbatch of this application. Use a small-scale spinning machine to produce filaments of about 150 denier / 28 filaments , And subsequently prepared as a fabric material.

Material 1: Add antibacterial masterbatch of this application;

Material 2: Add CN1111556C antibacterial masterbatch;

Material 3: No antibacterial masterbatch is added;

In order to test the heat-resistant water and washing and soaking resistance of the antibacterial fabric material of this application, materials 1 and 2 were further processed

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 ℃ Hours), rinse and dry;

The treated materials were not significantly damaged.

Example 3 Detection of antibacterial properties of textile materials

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.

Table 1 Antibacterial / Candida albicans properties of fabric materials

* Reference standard, below 90% cannot be said to have antibacterial effect.

Table 2. Anti-fungal properties of textile materials

Sample serial number	Aspergillus niger growth
Material 1	No growth
Material 2	No growth
Material 3	Macro growth
Material 1-1	No growth
Material 2-1	Microscopic growth
Material 1-2	No growth
Material 2-2	Macro growth

* Three growth criteria: no growth: invisible, microscopic growth: visible under the microscope, macroscopic growth: visible to the naked eye.

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.

Additional experiments have shown that the mechanical and antibacterial properties of the fabric material containing the antibacterial polymer of Example 1 (1.2) are similar to those of the fabric containing Example 1 (1.1), and the non-fabric fabric made has similar resistance to hot water immersion and washing Ability (to save time and cost without commissioning a complete test).

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.

The fabric material formulation and preparation process in the above embodiments are just for example. The antibacterial effect of the technical solution of the remaining fabric masterbatch such as nylon, polyester, etc., and other auxiliary materials combined with the antibacterial masterbatch of this application can be obtained from Example 2. 3, reasonable expectations, and these technical solutions are also within the scope of the disclosure and protection claimed in this application.

Claims (2)

1. An antibacterial fabric material, which includes an antibacterial polymer, wherein the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

   

   Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 active unsaturated double bond C5-C20 ester or ether groups; Z is H or X, the antibacterial polymer is prepared according to the following method: 124g of ethylene glycol and 260g of guanidine nitrate are added to the reaction kettle and mixed evenly Under the protection of nitrogen, the pH was adjusted to 5, heated to 120 ° C, reacted for 3h, and then 30g of acrylic acid was added to carry out the esterification reaction for 1h to complete the reaction.
2. An antibacterial fabric material, which includes an antibacterial polymer, wherein the antibacterial polymer is formed by polymerizing a polyhydric alcohol and a guanidine salt, and has the following structure:

   

   Wherein n = 5-10, m = 50-150; Y - is selected from _{^{Cl -, NO 3 -, HCO}} 3 -, CH 3 COO -, HSO 4 - or H ₂ PO ₄ ^- anion; X is containing 1- 5 active unsaturated double bond C5-C20 ester or ether groups; Z is H or X, the antibacterial polymer is prepared according to the following method: take 152g propylene glycol, 254g guanidine carbonate, add to the reaction kettle, mix evenly, nitrogen Under protection, the pH was adjusted to 4, heated to 130 ° C, and reacted for 2.5 hours. Then, 25 g of methacrylic acid was added to carry out the esterification reaction for 1.5 hours to complete the reaction.