Background
With the increase of health importance of people, the antibacterial functional requirements are also put forward on the textiles, and the antibacterial effect of the textiles is mainly realized by the antibacterial fibers. The antibacterial fiber has antibacterial and bactericidal functions, can prevent infection and infection, and is widely used for home textiles, underwear, sport shirts and the like, in particular to clothes for the old, pregnant and lying-in women and infants. The clothes made of the fiber have good antibacterial performance, and can resist the attachment of bacteria on clothes, so that people can be far away from the invasion of germs. The antibacterial fiber's resistance to and killing of bacteria is not a one-time temporary effect, but rather a long-term effect of weeks to years. The long-term antibacterial property is realized because the built-in design is adopted, so that the antibacterial agent can be slowly dissolved out, a bacteriostatic ring is formed on the surface of the fiber, and even if the surface antibacterial agent is washed away, a new antibacterial agent overflows to form a new bacteriostatic ring. Therefore, clothes made of the fiber have good washing fastness. Currently, there are many research institutes around the world developing new antibacterial fibers, and artificial antibacterial fibers are generally achieved by post-finishing or in-situ addition. The after-finishing is prepared by soaking natural fiber with organic antibacterial agent such as quaternary ammonium compound or fatty imide, and can be used for hospital textiles such as clothes, bed sheet, cover cloth, curtain, panty-hose, socks, bandage, etc. The in-situ addition is obtained by mixing inorganic antibacterial agent with heat resistance such as ceramic powder containing silver, copper and zinc ions into polyester, polyamide or polyacrylonitrile for spinning. The in-situ addition has a larger market for better durability and washability. The antibacterial agents are divided into two categories, one is organic antibacterial agents such as quaternary ammonium salts and guanidines, and the other is inorganic antibacterial agents such as zeolite, silica gel, phosphoric acid and the like loaded with silver, copper, zinc ions and the like. Among them, silver ion antibacterial agents are highly effective antibacterial agents and very safe to human bodies, and are widely used for the production of antibacterial fibers.
The nylon is the second largest fiber with the second yield of terylene in chemical fiber, has good hygroscopicity and good affinity with human body, is used for underwear, swimwear, socks, woven belts and the like, and the silver ion antibacterial agent is also used in the nylon. However, chinlon using silver ion antibacterial agent is very easy to discolor in the process of processing and using. When the fiber is placed for too long time or the pH value of the environment changes, the fiber can generate color changes such as red, brown and the like, and the fabric can generate uneven color spots, color blocks and the like, thereby seriously influencing the application field of the antibacterial nylon fiber. The main reason for the discoloration is that the precipitation speed of silver ions in the supported antibacterial agent is too high, and particularly in a high-temperature and high-humidity environment, the precipitated silver ions generate colored compounds to cause color change of fibers or fabrics, and the discoloration phenomenon is particularly obvious in chinlon 6 or chinlon 66.
The invention patent CN00800536.2 in China adds magnesium aluminum hydrotalcite in the antibacterial composition, which can inhibit the discoloration of the plastic product containing silver-based antibacterial agent, and the hydrotalcite has low price, but the effect of the hydrotalcite in the textile is unknown. The Chinese invention patent CN2005100109965 provides an anti-tarnish inorganic antibacterial agent, which is prepared by dispersing silver-zinc mixed solution in silica gel solution, sintering to embed silver ions in crystal lattices, thereby reducing silver precipitation and oxidation, improving discoloration, and having good antibacterial property and anti-tarnish effect, but the preparation process is complex. In summary, an antibacterial agent with excellent performance or a simple process is lacked at present to enable the nylon fiber to have antibacterial performance and good discoloration resistance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the color-changing-resistant antibacterial polyamide fiber.
In order to achieve the aim, the invention adopts the following technical scheme:
a color-change-resistant antibacterial nylon fiber is mainly prepared from nylon and antibacterial master batch according to the weight ratio of 100: 1-10; the antibacterial master batch comprises the following raw materials in percentage by weight: 70-95% of long carbon chain nylon and 5-30% of silver-carrying ion antibacterial agent.
Preferably, the discoloration-resistant antibacterial nylon fiber further comprises at least one of a dispersant, an antioxidant and a light stabilizer.
Preferably, the long carbon chain nylon is nylon with the average carbon chain length of more than 10 and the viscosity of 1.6-3.2.
Further preferably, the viscosity of the long-chain nylon is 2.0 to 2.8.
Further preferably, the long carbon chain nylon is selected from at least one of PA11, PA12, PA1010 and PA 1212.
Preferably, the silver-loaded ionic antimicrobial agent is selected from at least one of silver-loaded zirconium phosphate, silver-loaded zeolite, silver-loaded diatomaceous earth, silver-loaded silica, silver-loaded titania, and silver-loaded glass.
Further preferably, the dispersant is selected from at least one of amide wax and ester wax, metal stearate, and ethylene copolymer, which are available for nylon. The dispersing agent comprises ethylene bis stearamide wax, ethylene bis lauramide wax, pentaerythritol stearate, glyceryl monostearate, glyceryl tristearate, barium stearate, zinc stearate, calcium stearate, magnesium stearate, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer and polyoxyethylene wax; the content of the color-changing resistant antibacterial polyamide fiber is 0.01-1.0% of the total weight of the color-changing resistant antibacterial polyamide fiber.
Further preferably, the antioxidant is selected from at least one of hindered phenols and phosphites, including esters selected from the group consisting of N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine (antioxidant 1098), pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), diethyleneglycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (antioxidant 245), 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114), 1,3, 5-trimethyl-2, one or a mixture of more of 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 1330), 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione (antioxidant 1790) and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114), wherein the content of the antioxidant is 0.01-1.0% of the total weight of the discoloration-resistant antibacterial nylon fiber.
More preferably, the light stabilizer is selected from one or more of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitrile, triazines and hindered amines, and the content of the light stabilizer is 0.01-1.0% of the total weight of the discoloration resistant antibacterial polyamide fiber.
Preferably, the chinlon is selected from at least one of chinlon 6 and chinlon 66. More preferably, the chinlon is selected from chinlon 6.
The preparation method of the discoloration-resistant antibacterial polyamide fiber comprises the following steps:
(1) weighing long-chain nylon, a silver ion-loaded antibacterial agent, a dispersing agent, an antioxidant and a light stabilizer, melting, blending, extruding and granulating to obtain master batches;
(2) and (2) adding the master batch prepared in the step (1) and the nylon chips into a spinning machine together, and spinning the color-change-resistant nylon fiber.
Preferably, the granulator comprises a twin screw extruder, a single screw extruder and a b ü chner mixer.
Preferably, the extrusion temperature is 180-260 ℃.
The mass ratio of the long carbon chain nylon to the supported silver nylon antibacterial agent in the color-change-resistant antibacterial nylon fiber is 5-30: 95-70, if the ratio of the two components is too low, the addition amount is too high during spinning, the dispersion of long-chain nylon is not good, and the spinning broken ends are more; if the proportion of the two is too high, the master batch is difficult to disperse during preparation, and the spinning pressure rise is fast. Dispersing agent, antioxidant, light stabilizer, etc. are added to improve dispersion and oxidation resistance.
The main body of the antibacterial master batch is long-chain nylon, and the antibacterial master batch is blended with the nylon during spinning, so that the problems of fiber discoloration and the like are solved because the antibacterial master batch adopts a specific carrier different from that of spinning.
The invention has the advantages of
1. The raw materials are easy to obtain, the preparation process is simple, and the prepared nylon fiber has stable and lasting antibacterial performance;
2. the master batch adopts a specific carrier different from spinning, the master batch main body is long-chain nylon, and the master batch is blended with the nylon during spinning, so that the problem of fiber discoloration is solved;
3. the antibacterial nylon fiber prepared by the invention hardly changes color in the processing and using processes, and has excellent color change resistance;
4. the invention has wide application prospect, and the prepared antibacterial fiber can be effectively applied to the fields of socks, masks, household textiles, clothes, military combat clothes and the like.
Detailed Description
The formula of the antibacterial masterbatch in the antibacterial nylon fiber of examples 1-5 and comparative examples 1-3 is shown in table 1, and the addition amounts of the antibacterial masterbatch and nylon in the antibacterial nylon fiber of examples 1-5 and comparative examples 1-3 are shown in table 2.
Example 1
Mixing 8.5 kg of PA12 and 1.5 kg of silver-loaded zeolite antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperature is 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, water-cooling and bracing into antibacterial master batches, drying for 8 hours at 100 ℃, and adding the antibacterial master batches into PA6 according to a proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Example 2
Mixing 7.5 kg of PA12 with 2.5 kg of silver-loaded zeolite antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperature is 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, water-cooling and bracing into antibacterial master batches, drying for 8 hours at 100 ℃, and adding the antibacterial master batches into PA6 according to a proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Example 3
Mixing 8.5 kg of PA11 with 1.5 kg of silver-loaded zirconium phosphate antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperatures are 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃ and 230 ℃, water-cooling bracing and cutting into antibacterial master batches, drying for 8 hours at 100 ℃, and adding the antibacterial master batches into PA6 according to a proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Example 4
Mixing 7.5 kg of PA11 with 2.5 kg of silver-loaded zirconium phosphate antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperatures are 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃ and 230 ℃, water-cooling and drawing into antibacterial master batches, drying for 8 hours at 100 ℃, adding the antibacterial master batches into PA6 in proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Example 5
7.5 kg of PA12, 2.5 kg of silver-loaded zirconium phosphate antibacterial agent, 50 g of dispersing agent EBS, 20 g of antioxidant 1098 and 20 g of light stabilizer 622 are mixed, a double-screw extruder with the screw diameter of 35 is adopted for extrusion and granulation, the screw temperature is respectively 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, water-cooling bracing is carried out to cut antibacterial master batches, the drying is carried out for 8 hours at the temperature of 100 ℃, the antibacterial master batches are added into PA6 for spinning according to the proportion, the antibacterial PA6 yarn with the specification of 70d/24f is obtained, and the antibacterial PA6 yarn with the antibacterial agent content of 1 percent is obtained.
Comparative example 1
Mixing 7.5 kg of PA6 with 2.5 kg of silver-loaded zeolite antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperature is 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, water-cooling and bracing into antibacterial master batches, drying for 8 hours at 100 ℃, and adding the antibacterial master batches into PA6 according to a proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Comparative example 2
Mixing 7.5 kg of PA6 with 2.5 kg of silver-loaded zirconium phosphate antibacterial agent, extruding and granulating by using a double-screw extruder with the screw diameter of 35, wherein the screw temperatures are 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃ and 230 ℃, water-cooling and drawing into antibacterial master batches, drying for 8 hours at 100 ℃, adding the antibacterial master batches into PA6 in proportion for spinning to obtain 70d/24f antibacterial PA6 yarn with the antibacterial agent content of 1 percent.
Comparative example 3
Mixing 7.5 kg of PA6 with 2.5 kg of silver-loaded zirconium phosphate antibacterial agent, 50 g of dispersing agent EBS, 20 g of antioxidant 1098 and 20 g of light stabilizer 622, extruding and granulating by adopting a double-screw extruder with the diameter of a screw of 35, wherein the screw temperature is 230 ℃, 240 ℃, 250 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, water-cooling bracing into antibacterial master batches, drying for 8 hours at 100 ℃, and adding the antibacterial master batches into PA6 for spinning to obtain the antibacterial PA6 yarn with the antibacterial agent content of 1 percent and the specification of 70d/24 f.
The antibacterial nylon fibers prepared in examples 1 to 5 and comparative examples 1 to 3 were woven into a sock cylinder, and then the antibacterial rate was measured by AATCC 100, after spinning into a pre-oriented yarn, the south was left outdoors for 10 days, the outer layer was woven into a sock cylinder, and the color before and after the left was measured by a color meter to obtain Δ E, and the results are shown in table 3.
TABLE 1 formulation (weight percent) of antibacterial masterbatch in antibacterial nylon fiber of examples 1-5 and comparative examples 1-3
TABLE 2 addition amounts (weight ratio) of antibacterial mother particles and nylon in antibacterial nylon fibers of examples 1-5 and comparative examples 1-3
TABLE 3 results of antibacterial and discoloration-resistant tests of antibacterial nylon fibers of examples 1-5 and comparative examples 1-3
Remarking: and the delta E is the color difference value and represents the size of the color difference.
As can be seen from Table 3, the antibacterial nylon fibers prepared in examples 1-5 have excellent antibacterial performance, hardly change color during processing and use, and have better color change resistance than the antibacterial nylon fibers prepared in comparative examples 1-3.
The above examples are merely illustrative for clarity and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.