Antibacterial and environmentally friendly dyed fiber and preparation method thereof

Abstract

The present invention discloses an antibacterial and environmentally friendly dyed fiber and a preparation method thereof, relating to the field of dyed fiber technology. The fiber comprises a composite fiber system consisting of modified cotton fiber, modified nylon fiber, and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, modified nylon fiber, and modified polyester fiber is 30-40:20-25:15-25. The antibacterial and environmentally friendly dyed fiber also comprises silver ions, copper ions, and zinc ions. The present invention utilizes a synergistic antibacterial mechanism through the sequential release of silver, copper, and zinc ions. Silver ions are rapidly released within the first 6 hours, achieving an instantaneous bactericidal effect; copper ions are continuously released within 6-48 hours, maintaining a medium-term antibacterial effect; and zinc ions provide sustained-release protection for up to 7 days.

Description

Technical Field

[0001] The present invention relates to the technical field of dyed fibers, in particular to an antibacterial and environmentally friendly dyed fiber and a preparation method thereof. Background Art

[0002] With the improvement of people's living standards and the strengthening of health awareness, the functional requirements of textiles are increasing. Traditional antimicrobial fibers mainly achieve antimicrobial function by adding a single antimicrobial agent during the fiber preparation process or using a post-finishing process, while also imparting color effects to the fibers through chemical dyeing processes. However, with increasingly stringent environmental regulations and consumers' increasing demands for product safety, traditional antimicrobial dyed fiber technology faces many challenges, such as single function, poor environmental protection, and insufficient durability. There is an urgent need to develop new multifunctional composite antimicrobial and environmentally friendly dyed fiber technologies.

[0003] The antibacterial dyeing fibers in the existing technology have the following significant defects: first, the antibacterial mechanism is single, and most products rely on only a single antibacterial component, which is prone to bacterial resistance, and the antibacterial spectrum is narrow, making it difficult to cope with complex microbial environments; moreover, the functional durability is poor, and the antibacterial and dyeing effects significantly decay after multiple washings, which cannot meet the needs of long-term use; in addition, the environmental performance is insufficient, a large amount of chemical dyes and antibacterial agents are used, the production process produces harmful waste, and the products are difficult to biodegrade, causing secondary pollution to the environment; finally, there is a lack of coordinated design between different functional components, and each component acts independently, and it is impossible to achieve synergistic enhancement of functions, the overall performance improvement is limited, and it is easy for components to interfere with each other, affecting the comprehensive performance of the fiber. Summary of the Invention

[0004] In view of the problems existing in the existing antibacterial and environmentally friendly dyed fibers and preparation methods thereof, the present invention is proposed.

[0005] Therefore, the problem to be solved by the present invention is that the traditional antibacterial dyed fibers have a single antibacterial mechanism, poor functional durability, and are not environmentally friendly.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] In a first aspect, an embodiment of the present invention provides an antibacterial and environmentally friendly dyed fiber, comprising a composite fiber system consisting of modified cotton fiber, modified nylon fiber, and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, the modified nylon fiber, and the modified polyester fiber is 30-40:20-25:15-25;

[0008] The antibacterial and environmentally friendly dyed fiber also includes silver ions, copper ions, and zinc ions;

[0009] The composite fiber system further comprises the following functional additives in parts by weight:

[0010] Modified chitosan: 6-8 parts;

[0011] Modified attapulgite: 5-8 parts;

[0012] Natural plant dyes: 3-5 parts;

[0013] Zeolite powder: 1-3 parts;

[0014] Seaweed polysaccharide: 1-2 parts;

[0015] Cross-linking agent: 5-7 parts.

[0016] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the modified cotton fiber is prepared by impregnation with a titanium-containing silicone oil emulsion and then drying;

[0017] The modified nylon fiber is prepared by treating a coupling agent mixture and then drying the mixture;

[0018] The modified polyester fiber is prepared after pretreatment with an antibacterial and mildew-proof finishing agent.

[0019] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the titanium-containing silicone oil emulsion is prepared according to the following method:

[0020] Add 3-5 parts of Span 60 to 30-50 parts of dichloromethane according to weight;

[0021] At 40°C, add 1-2 parts of butyl titanate and 1-2 parts of composite silicone oil while stirring, then add 0.5-2 parts of silane coupling agent KH560 and 0.5-2 parts of emulsifier N in sequence, and then stir evenly;

[0022] Then add 60 to 100 parts of water, continue stirring at 40°C for 40 minutes, then heat to 60°C and stir thoroughly to obtain a titanium-containing silicone oil emulsion;

[0023] Wherein, the composite silicone oil is a mixture of alkyl-modified silicone oil and polyether-modified silicone oil, and the weight ratio of alkyl-modified silicone oil to polyether-modified silicone oil is 1:0.5-2;

[0024] The composite silicone oil also includes hydroxy safflower yellow pigment A, and the ratio of the composite silicone oil to the hydroxy safflower yellow pigment A is 10:1-3.

[0025] The preparation process of titanium-containing silicone oil emulsion ensures the stable combination of titanium ions and silicone oil, which not only provides photocatalytic antibacterial function, but also improves the fiber feel and hydrophobic properties. At the same time, hydroxysafflor yellow A enhances the natural antioxidant activity.

[0026] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the preparation method of the alkyl-modified silicone oil is as follows:

[0027] Mix isododecane and dimethyl silicone oil in a weight ratio of 2:1 to 1.5;

[0028] After stirring evenly, add potassium hydroxide in an amount of 0.01 to 0.02 times the weight of isododecane to carry out a catalytic reaction, raise the temperature to 100 to 150° C., and continue the reaction until the system becomes a solid-liquid mixture;

[0029] Then the temperature is lowered to 10-20° C., filtered, washed with water until neutral, and then dried to obtain alkyl-modified silicone oil.

[0030] The synthesis process of alkyl-modified silicone oil ensures the controllable modification of silicone oil chain segments, improves the compatibility and bonding strength with the fiber substrate, and enhances the durability of the antibacterial function.

[0031] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the coupling agent mixture is prepared according to the following method:

[0032] Add 1g of coupling agent to 10ml of citric acid solution and mix with a citric acid solution with a concentration of 0.04-0.25g / L;

[0033] Then, ethanol was added and stirred to obtain a coupling agent mixture;

[0034] The ratio of the citric acid solution to ethanol is 100:2-5;

[0035] The coupling agent is a composite system of a titanate coupling agent and a zirconium-aluminum coupling agent;

[0036] The titanate coupling agent is selected from Y-570 or BY-T6102, the zirconium-aluminum coupling agent is selected from TMC-101 or TMC-102, and the weight ratio of the titanate coupling agent to the zirconium-aluminum coupling agent is 1:0.3-0.8.

[0037] Through the synergistic effect of titanate and zirconium-aluminum coupling agent, an interpenetrating network structure is formed on the fiber surface, which significantly improves the interface bonding strength and washing resistance.

[0038] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the antibacterial and mildew-proof finishing agent is composed of a base polymer component and a functional polymer component;

[0039] The base polymer component includes: 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2.5 parts of zinc methacrylate, 1.2 parts of 2,4-dimethoxyphenol, and 1.5 parts of an azo initiator, and is dispersed in 100 parts of ethyl acetate;

[0040] The functional polymer component includes: 18 parts of tricyanoglyceryl ether propyl trimethoxysilane, 2-4 parts of nano titanium dioxide, and 0.5-1 parts of penetration enhancer.

[0041] The penetration enhancer is an ammonia solution with a concentration of 20-25%.

[0042] The compound design of the basic polymer component and the functional polymer component realizes the integration of multiple functions of mildew prevention, antibacterial and penetration promotion, thereby improving the comprehensive efficacy and depth of action of the antibacterial and mildew prevention finishing agent.

[0043] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the modified chitosan is chitosan that is double-modified by thiolation and imidazoleization, and the preparation method thereof comprises:

[0044] Dissolve the basic chitosan in a hydrochloric acid solution, add sodium periodate oxidant, stir at a speed of 100-200 r / min, and obtain the mercapto-containing chitosan by filtering;

[0045] In a reaction vessel, add mercaptochitosan and anhydrous butanol, stir, then add polyethylene glycol diglycidyl ether, maintain the temperature at 50-55°C, react for 1-2 hours, filter under reduced pressure, wash and dry to obtain an intermediate;

[0046] Anhydrous butanol was added to the reaction vessel, and after stirring evenly at 10-15°C, sodium cyanoborohydride reducing agent was slowly added. After reacting for 1-2 hours, the modified chitin was obtained by filtration under reduced pressure;

[0047] 2-Mercaptoimidazole is added to a 0.2-0.3 mol / L hydrochloric acid solution, and the modified chitin is added after stirring. After reacting for 15-20 hours, the modified chitosan is obtained, and the molecular weight is 55,000-70,000.

[0048] Chitosan modified with both thiolation and imidazole groups exhibits enhanced antibacterial activity and improved dye binding ability while maintaining good biocompatibility and degradability.

[0049] As a preferred embodiment of the antibacterial and environmentally friendly dyed fiber of the present invention, the preparation method of the modified attapulgite comprises:

[0050] Calcine the basic attapulgite at 700-800℃ for 1-2h and grind it into 80-100 mesh particles;

[0051] Then add 6-10% mass fraction of dilute hydrochloric acid, the weight ratio of basic attapulgite to dilute hydrochloric acid is 1:3-5, stir at 65-75℃ for 1-2h, filter and wash, dry, and re-grind into 60-80 mesh particles;

[0052] Then, the modified attapulgite is immersed in a solution of octadecanoic acid and ethanol in a weight ratio of 1:20-30, stirred at 85-110° C. for 3-5 hours, filtered and washed, and then dried at 50-60° C. to obtain the modified attapulgite.

[0053] In a second aspect, an embodiment of the present invention provides a method for preparing an antibacterial and environmentally friendly dyed fiber, which comprises the following steps:

[0054] preparing titanium-containing silicone oil emulsion, coupling agent mixture, and antibacterial and mildew-proof finishing agent;

[0055] The titanium-containing silicone oil emulsion is evenly sprayed on the surface of the cotton fiber, with the spraying amount being 8-12% of the weight of the cotton fiber, and treated at 60-80°C for 30-45 minutes to obtain modified cotton fiber;

[0056] The coupling agent mixture is sprayed on the surface of the nylon fiber in an atomized manner, with the spraying amount being 5-8% of the weight of the nylon fiber, and treated at 50-70°C for 20-30 minutes to obtain the modified nylon fiber;

[0057] The antibacterial and mildew proof finishing agent is sprayed on the surface of the polyester fiber in an amount of 10-15% of the weight of the polyester fiber, and treated at 80-100° C. for 40-60 minutes to obtain a modified polyester fiber;

[0058] Disperse the modified cotton fiber in a silver nitrate solution, shake and disperse at 80-85°C for 5-10 hours, filter and dry to complete the silver ion loading;

[0059] The modified attapulgite was placed in a copper chloride solution, shaken and dispersed at 65-70°C for 2-4 hours, filtered and dried to complete the copper ion loading;

[0060] Soak the zeolite powder in zinc sulfate solution at a weight ratio of 1:4-6, let it stand for 2-3 hours, then filter and dry to complete the zinc ion loading;

[0061] Modified cotton fiber, modified nylon fiber and modified polyester fiber loaded with silver ions were weighed and mixed with functional additives. Antibacterial and environmentally friendly dyed fibers were prepared through opening, mixing, carding, drawing, woolen spinning and worsted spinning processes.

[0062] As a preferred embodiment of the method for preparing the antibacterial and environmentally friendly dyed fiber of the present invention, the concentration of the silver nitrate solution is 0.1-0.5 mol / L, the concentration of the copper chloride solution is 0.05-0.2 mol / L, and the concentration of the zinc sulfate solution is 0.1-0.3 mol / L.

[0063] The beneficial effects of the present invention are:

[0064] By compounding modified cotton, modified nylon, and modified polyester fibers in a precise mass ratio of 30-40:20-25:15-25, a unique three-dimensional network structure is formed, in which each fiber performs a specific function: cotton fibers are responsible for antibacterial and improved hand feel, nylon fibers provide interfacial bonding and mechanical properties, and polyester fibers are responsible for mildew resistance and durability. This differentiated functional division avoids the mutual interference of different functional components in traditional composite materials, achieving a synergistic effect of 1+1+1 greater than 3.

[0065] The present invention utilizes a synergistic antibacterial mechanism through the sequential release of silver, copper, and zinc ions. Silver ions are rapidly released within the first six hours, achieving an instantaneous bactericidal effect; copper ions are continuously released for 6-48 hours, maintaining a medium-term antibacterial effect; and zinc ions provide sustained-release protection for up to seven days. This sequential ion release pattern, unlike the instantaneous, high-volume release of traditional antibacterial materials, not only prevents the development of bacterial resistance but also keeps the total metal ion release within a safe range, resolving the difficult balance between antibacterial efficacy and biosafety.

[0066] Through the emulsification process of butyl titanate and composite silicone oil, a nanoscale titanium and silicon composite micelle structure is formed. Under ultraviolet light excitation, hydroxyl radicals are generated, achieving a photocatalytic antibacterial effect. Furthermore, hydroxysafflor yellow A not only provides a natural dyeing effect, but also forms a coordination complex with titanium ions, which can also stimulate antibacterial activity under visible light, extending the effective antibacterial time from the traditional ultraviolet light exposure period to all-day.

[0067] Modified attapulgite, activated by calcination at 700-800°C and treated with octadecanoic acid for hydrophobicity, exhibits excellent metal ion carrier properties. The calcination process not only removes structural water but also increases the specific surface area of ​​the attapulgite by 40-60%, significantly enhancing its ion exchange capacity. The surface modification with octadecanoic acid improves the dispersibility of the attapulgite in the organic phase. The resulting hydrophobic surface layer acts as a controlled-release membrane, resulting in ideal zero-order kinetics for the release of loaded copper ions. DETAILED DESCRIPTION

[0068] To make the above-mentioned objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with specific embodiments of the present invention. It is obvious that the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary persons in this field without creative work should fall within the scope of protection of the present invention.

[0069] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0070] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0071] Example 1

[0072] An antibacterial and environmentally friendly dyed fiber comprises a composite fiber system consisting of modified cotton fiber, modified nylon fiber and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, the modified nylon fiber and the modified polyester fiber is 30:20:15;

[0073] Antibacterial and eco-friendly dyed fibers also include silver, copper, and zinc ions;

[0074] The composite fiber system further comprises the following functional additives in parts by weight: modified chitosan: 6 parts; modified attapulgite: 5 parts; natural plant dye: 3 parts; zeolite powder: 1 part; seaweed polysaccharide: 1 part; and cross-linking agent: 5 parts.

[0075] The modified cotton fiber is prepared by impregnation with titanium-containing silicone oil emulsion and then drying; the modified nylon fiber is prepared by treatment with coupling agent mixture and then drying; and the modified polyester fiber is prepared by pretreatment with antibacterial and mildew-proof finishing agent.

[0076] The titanium-containing silicone oil emulsion is prepared as follows:

[0077] 3 parts of Span 60 are added to 30 parts of dichloromethane according to weight; 1 part of butyl titanate and 1 part of composite silicone oil are added while stirring at 40°C, and then 0.5 parts of silane coupling agent KH560 and 0.5 parts of emulsifier N are added in sequence, and then stirred evenly; 60 parts of water are added, and stirring is continued at 40°C for 40 minutes, and then heated to 60°C and stirred thoroughly to obtain a titanium-containing silicone oil emulsion; wherein the composite silicone oil is a mixture of alkyl-modified silicone oil and polyether-modified silicone oil, and the weight ratio of alkyl-modified silicone oil to polyether-modified silicone oil is 1:0.5; the composite silicone oil also includes hydroxysafflor yellow A, and the ratio of composite silicone oil to hydroxysafflor yellow A is 10:1.

[0078] The preparation method of alkyl modified silicone oil is:

[0079] Mix isododecane and dimethyl silicone oil in a weight ratio of 2:1; after stirring evenly, add 0.01 times the weight of isododecane of potassium hydroxide to carry out a catalytic reaction, increase the temperature to 100°C, and continue the reaction until the system becomes a solid-liquid mixture; then reduce the temperature to 10°C, filter, wash with water until neutral, and then dry to obtain alkyl-modified silicone oil.

[0080] The coupling agent mixture was prepared as follows:

[0081] The coupling agent is added to a citric acid solution with a concentration of 0.04 g / L according to a ratio of 1 g of coupling agent to 10 ml of citric acid solution, and then ethanol is added and stirred to obtain a coupling agent mixture; the ratio of citric acid solution to ethanol is 100:2; the coupling agent is a composite system of a titanate coupling agent and a zirconium-aluminum coupling agent; wherein the titanate coupling agent is selected from Y-570, the zirconium-aluminum coupling agent is selected from TMC-101, and the weight ratio of the titanate coupling agent to the zirconium-aluminum coupling agent is 1:0.3.

[0082] The antibacterial and antifungal finishing agent is composed of a basic polymer component and a functional polymer component;

[0083] The basic polymer components include: 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2.5 parts of zinc methacrylate, 1.2 parts of 2,4-dimethoxyphenol, and 1.5 parts of azo initiator, and are dispersed in 100 parts of ethyl acetate; the functional polymer components include: 18 parts of tricyanoglycerol glycidyl ether propyltrimethoxysilane, 2 parts of nano titanium dioxide, and 0.5 parts of penetration enhancer, which is an ammonia solution with a concentration of 20-25%.

[0084] The modified chitosan is chitosan that is double-modified by thiolization and imidazoleization, and the preparation method thereof comprises:

[0085] The basic chitosan was dissolved in a hydrochloric acid solution, sodium periodate oxidant was added, the mixture was stirred at a speed of 100 r / min, and mercapto chitosan was obtained by filtration; mercapto chitosan and anhydrous butanol were added to a reaction vessel, and polyethylene glycol diglycidyl ether was added after stirring. The temperature was maintained at 50°C, and the mixture was reacted for 1 hour. The mixture was then filtered under reduced pressure, washed, and dried to obtain an intermediate; anhydrous butanol was added to the reaction vessel, and after stirring at 10°C, sodium cyanoborohydride reducing agent was slowly added. After reacting for 1 hour, the mixture was filtered under reduced pressure to obtain modified chitosan; 2-mercaptoimidazole was added to a 0.2 mol / L hydrochloric acid solution, and the modified chitosan was added after stirring. The mixture was reacted for 15 hours to obtain modified chitosan with a molecular weight of 55,000.

[0086] The preparation method of modified attapulgite comprises:

[0087] The basic attapulgite was calcined at 700°C for 1 hour and ground into 80-mesh particles; then added into 6% by mass dilute hydrochloric acid, with the weight ratio of basic attapulgite to dilute hydrochloric acid being 1:3, stirred at 65°C for 1 hour, filtered and washed, dried, and re-ground into 60-mesh particles;

[0088] Then, the mixture was immersed in a solution of octadecanoic acid and ethanol in a weight ratio of 1:20, stirred at 85°C for 3 hours, filtered, washed, and then dried at 50°C to obtain modified attapulgite.

[0089] Example 2

[0090] An antibacterial and environmentally friendly dyed fiber comprises a composite fiber system consisting of modified cotton fiber, modified nylon fiber and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, the modified nylon fiber and the modified polyester fiber is 35:22:20;

[0091] Antibacterial and eco-friendly dyed fibers also include silver, copper, and zinc ions;

[0092] The composite fiber system further comprises the following functional additives in parts by weight: modified chitosan: 7 parts; modified attapulgite: 6 parts; natural plant dye: 4 parts; zeolite powder: 2 parts; seaweed polysaccharide: 1 part; and cross-linking agent: 6 parts.

[0093] The modified cotton fiber is prepared by impregnation with titanium-containing silicone oil emulsion and then drying; the modified nylon fiber is prepared by treatment with coupling agent mixture and then drying; and the modified polyester fiber is prepared by pretreatment with antibacterial and mildew-proof finishing agent.

[0094] The titanium-containing silicone oil emulsion is prepared as follows:

[0095] 4 parts of Span 60 are added to 40 parts of dichloromethane according to weight; 1 part of butyl titanate and 1 part of composite silicone oil are added while stirring at 40°C, and then 1 part of silane coupling agent KH560 and 1 part of emulsifier N are added in sequence, and then stirred evenly; 80 parts of water are added, and stirring is continued at 40°C for 40 minutes, and then heated to 60°C and stirred thoroughly to obtain a titanium-containing silicone oil emulsion; wherein the composite silicone oil is a mixture of alkyl-modified silicone oil and polyether-modified silicone oil, and the weight ratio of alkyl-modified silicone oil to polyether-modified silicone oil is 1:1; the composite silicone oil also includes hydroxysafflor yellow A, and the ratio of composite silicone oil to hydroxysafflor yellow A is 10:2.

[0096] The preparation method of alkyl modified silicone oil is:

[0097] Mix isododecane and dimethyl silicone oil in a weight ratio of 2:1.2; after stirring evenly, add 0.01 times the weight of isododecane potassium hydroxide to carry out a catalytic reaction, increase the temperature to 120°C, and continue the reaction until the system becomes a solid-liquid mixture; then reduce the temperature to 15°C, filter, wash with water until neutral, and then dry to obtain alkyl-modified silicone oil.

[0098] The coupling agent mixture was prepared as follows:

[0099] The coupling agent is added to a citric acid solution with a concentration of 0.15 g / L according to a ratio of 1 g of coupling agent to 10 ml of citric acid solution, and the mixture is mixed; ethanol is then added, and the mixture is stirred to obtain a coupling agent mixture; the ratio of the citric acid solution to the ethanol is 100:2; the coupling agent is a composite system of a titanate coupling agent and a zirconium-aluminum coupling agent; wherein the titanate coupling agent is selected from BY-T6102, the zirconium-aluminum coupling agent is selected from TMC-101, and the weight ratio of the titanate coupling agent to the zirconium-aluminum coupling agent is 1:0.5.

[0100] The antibacterial and antifungal finishing agent is composed of a basic polymer component and a functional polymer component;

[0101] The basic polymer components include: 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2.5 parts of zinc methacrylate, 1.2 parts of 2,4-dimethoxyphenol, and 1.5 parts of azo initiator, and are dispersed in 100 parts of ethyl acetate; the functional polymer components include: 18 parts of tricyanoglycerol glycidyl ether propyltrimethoxysilane, 3 parts of nano titanium dioxide, and 0.7 parts of penetration enhancer, which is a 22% ammonia solution.

[0102] The modified chitosan is chitosan that is double-modified by thiolization and imidazoleization, and the preparation method thereof comprises:

[0103] The basic chitosan was dissolved in a hydrochloric acid solution, sodium periodate oxidant was added, the mixture was stirred at a speed of 150 r / min, and mercapto chitosan was obtained by filtration; mercapto chitosan and anhydrous butanol were added to a reaction vessel, and polyethylene glycol diglycidyl ether was added after stirring. The temperature was maintained at 52°C, and the mixture was reacted for 1 hour. The mixture was then filtered under reduced pressure, washed, and dried to obtain an intermediate; anhydrous butanol was added to the reaction vessel, and after stirring at 13°C, sodium cyanoborohydride reducing agent was slowly added. After reacting for 1 hour, the mixture was filtered under reduced pressure to obtain modified chitosan; 2-mercaptoimidazole was added to a 0.2 mol / L hydrochloric acid solution, and the modified chitosan was added after stirring. After reacting for 17 hours, modified chitosan with a molecular weight of 65,000 was obtained.

[0104] The preparation method of modified attapulgite comprises:

[0105] The basic attapulgite was calcined at 750°C for 1 hour and ground into 90-mesh particles; then added into 8% by mass dilute hydrochloric acid, with the weight ratio of basic attapulgite to dilute hydrochloric acid being 1:4, stirred at 70°C for 1 hour, filtered, washed, dried, and re-ground into 70-mesh particles;

[0106] Then, the mixture was immersed in a solution of octadecanoic acid and ethanol in a weight ratio of 1:25, stirred at 95° C. for 4 hours, filtered, washed, and then dried at 55° C. to obtain modified attapulgite.

[0107] Example 3

[0108] An antibacterial and environmentally friendly dyed fiber comprises a composite fiber system consisting of modified cotton fiber, modified nylon fiber and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, the modified nylon fiber and the modified polyester fiber is 40:25:25;

[0109] Antibacterial and eco-friendly dyed fibers also include silver, copper, and zinc ions;

[0110] The composite fiber system further comprises the following functional additives in parts by weight: modified chitosan: 8 parts; modified attapulgite: 8 parts; natural plant dye: 5 parts; zeolite powder: 3 parts; seaweed polysaccharide: 2 parts; and cross-linking agent: 7 parts.

[0111] The modified cotton fiber is prepared by impregnation with titanium-containing silicone oil emulsion and then drying; the modified nylon fiber is prepared by treatment with coupling agent mixture and then drying; and the modified polyester fiber is prepared by pretreatment with antibacterial and mildew-proof finishing agent.

[0112] The titanium-containing silicone oil emulsion is prepared as follows:

[0113] Add 5 parts of Span 60 to 50 parts of dichloromethane according to weight; add 2 parts of butyl titanate and 2 parts of composite silicone oil while stirring at 40°C, then add 2 parts of silane coupling agent KH560 and 2 parts of emulsifier N in sequence, and then stir evenly; then add 100 parts of water, continue stirring at 40°C for 40 minutes, then heat to 60°C and stir thoroughly to obtain a titanium-containing silicone oil emulsion; wherein the composite silicone oil is a mixture of alkyl-modified silicone oil and polyether-modified silicone oil, and the weight ratio of alkyl-modified silicone oil to polyether-modified silicone oil is 1:2; the composite silicone oil also includes hydroxysafflor yellow A, and the ratio of composite silicone oil to hydroxysafflor yellow A is 10:3.

[0114] The preparation method of alkyl modified silicone oil is:

[0115] Isododecane and dimethyl silicone oil are mixed in a weight ratio of 2:1.5; after stirring evenly, 0.02 times the weight of isododecane potassium hydroxide is added to carry out a catalytic reaction, the temperature is raised to 150°C, and the reaction is continued until the system becomes a solid-liquid mixture; then the temperature is lowered to 20°C, filtered, washed with water until neutral, and then dried to obtain alkyl-modified silicone oil.

[0116] The coupling agent mixture was prepared as follows:

[0117] The coupling agent is added to a citric acid solution with a concentration of 0.25 g / L according to a ratio of 1 g of coupling agent to 10 ml of citric acid solution, and then ethanol is added and stirred to obtain a coupling agent mixture. The ratio of the citric acid solution to the ethanol is 100:5. The coupling agent is a composite system of a titanate coupling agent and a zirconium-aluminum coupling agent. The titanate coupling agent is selected from BY-T6102, the zirconium-aluminum coupling agent is selected from TMC-102, and the weight ratio of the titanate coupling agent to the zirconium-aluminum coupling agent is 1:0.8.

[0118] The antibacterial and antifungal finishing agent is composed of a basic polymer component and a functional polymer component;

[0119] The basic polymer components include: 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2.5 parts of zinc methacrylate, 1.2 parts of 2,4-dimethoxyphenol, and 1.5 parts of azo initiator, and are dispersed in 100 parts of ethyl acetate; the functional polymer components include: 18 parts of tricyanoglycerol glycidyl ether propyltrimethoxysilane, 4 parts of nano titanium dioxide, and 1 part of penetration enhancer, which is a 25% ammonia solution.

[0120] The modified chitosan is chitosan that is double-modified by thiolization and imidazoleization, and the preparation method thereof comprises:

[0121] The basic chitosan was dissolved in a hydrochloric acid solution, sodium periodate oxidant was added, the mixture was stirred at a speed of 200 r / min, and mercapto chitosan was obtained by filtration; mercapto chitosan and anhydrous butanol were added to a reaction vessel, and polyethylene glycol diglycidyl ether was added after stirring. The temperature was maintained at 55°C, and the mixture was reacted for 2 hours. The mixture was then filtered under reduced pressure, washed, and dried to obtain an intermediate; anhydrous butanol was added to the reaction vessel, and after stirring at 15°C, sodium cyanoborohydride reducing agent was slowly added. After reacting for 2 hours, the mixture was filtered under reduced pressure to obtain modified chitosan; 2-mercaptoimidazole was added to a 0.3 mol / L hydrochloric acid solution, and the modified chitosan was added after stirring. After reacting for 17 hours, modified chitosan with a molecular weight of 70,000 was obtained.

[0122] The preparation method of modified attapulgite comprises:

[0123] The basic attapulgite was calcined at 800°C for 2 hours and ground into 100-mesh particles; then added into 10% by mass dilute hydrochloric acid, with the weight ratio of the basic attapulgite to the dilute hydrochloric acid being 1:5, stirred at 75°C for 2 hours, filtered, washed, dried, and re-ground into 80-mesh particles;

[0124] Then, the mixture was immersed in a solution of octadecanoic acid and ethanol in a weight ratio of 1:30, stirred at 110° C. for 4 hours, filtered, washed, and then dried at 60° C. to obtain modified attapulgite.

[0125] Comparative Example 1

[0126] Modified cotton fiber, modified nylon fiber, and modified polyester fiber were composited in an equal mass ratio (33.3:33.3:33.3) with the addition of the same functional additives: 7 parts modified chitosan, 6 parts modified attapulgite, 4 parts natural plant dye, 2 parts zeolite powder, 1 part seaweed polysaccharide, and 6 parts crosslinking agent. The modification methods for each fiber were the same as in Example 2.

[0127] Comparative Example 2

[0128] The same composite fiber system and mass ratio (35:22:20) as in Example 2 were used, but only silver ions were used as the antibacterial component, and the silver ion loading was adjusted to be equal to the total amount of the three metal ions in Example 2. The other functional additive compositions and preparation methods were the same as in Example 2.

[0129] Comparative Example 3

[0130] The same formula and preparation process as in Example 2 were used, except that the modified attapulgite was replaced by ordinary attapulgite that had not been calcined at high temperature and modified with octadecanoic acid, and the dosage remained unchanged at 6 parts.

[0131] Through experiments, the experimental results are shown in Table 1;

[0132] Table 1: Comparison of antibacterial performance tests

[0133] Test items Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Antibacterial rate against Escherichia coli (initial) 99.2% 95.2% 96.8% 94.7% Antibacterial rate against Staphylococcus aureus (initial) 96.8% 92.1% 94.5% 91.3% Antibacterial rate after 24 hours (Escherichia coli) 97.5% 89.3% 85.3% 88.1% Antibacterial rate after 7 days (Escherichia coli) 94.1% 82.7% 72.1% 79.8% Antibacterial duration (days) >7 4-5 3-4 4-5

[0134] The experimental steps included: Fiber samples prepared in Example 2 and three comparative examples were taken, with six replicates prepared for each group. The samples were tested at different time points, and the samples were humidified under standard conditions for 24 hours. Escherichia coli (ATCC8739) and Staphylococcus aureus (ATCC6538) were cultured in nutrient broth for 24 hours. 0.2 mL of bacterial solution was evenly dripped onto the surface of the fiber samples. The samples were placed in sterile Petri dishes and incubated in a 37°C incubator. Samples were collected for testing after 2 hours (initial), 24 hours, and 7 days of incubation. Antibacterial rate (%) = (number of bacteria in the control group - number of bacteria in the test group) / number of bacteria in the control group × 100%.

[0135] Example 2 showed the highest antibacterial rate in the early stage, which was mainly attributed to the synergistic activation of the triple antibacterial mechanism. Silver ions were preferentially released within the first 6 hours, directly destroying the bacterial cell wall and cell membrane, achieving an instantaneous killing effect; the titanium-containing silicone oil emulsion immediately produced hydroxyl radicals under inoculation light conditions, enhancing the initial bactericidal effect; the dual modification of thiolization and imidazoleization made the chitosan bind more tightly to the bacterial cell membrane, destroying the permeability of the cell membrane.

[0136] Comparative Example 1, using a formula with equal mass ratios, failed to achieve optimal coordination of the components, limiting initial antibacterial efficacy. While the silver ion content in Comparative Example 2 was comparable to that in Example 2, it lacked the synergistic effects of other antibacterial mechanisms. The unmodified attapulgite carrier in Comparative Example 3 was less effective, with unstable copper ion release, affecting initial antibacterial efficacy.

[0137] After 24 hours, Example 2 still maintained a high antibacterial rate of 97.5%, which was significantly better than all the comparative examples. This was because, when the release of silver ions tended to be flat, copper ions began to be continuously released, maintaining the mid-term antibacterial effect; the hydrophobic controlled-release membrane formed by high-temperature calcination and octadecanoic acid surface modification ensured the stable release of copper ions; the coordination complex formed by hydroxysafflor yellow A and titanium ions continued to produce antibacterial activity under visible light.

[0138] The data after 7 days best reflects the unique advantages of the technical solution of Example 2: zinc ions provide sustained-release protection for up to 7 days, ensuring long-term antibacterial effect; through reversible complexation with metal ions, environmental responsive release regulation is achieved; silver ions are loaded into modified cotton fibers, copper ions are loaded into modified attapulgite, and zinc ions are loaded into zeolite powder to achieve orderly release in space and time.

[0139] The single silver ion system in Comparative Example 2 showed an antibacterial rate of only 72.1%, the largest decrease, indicating the limitations of a single antibacterial mechanism. Although Comparative Examples 1 and 3 have multiple components, they lack a systematic sequential design, and the long-term effect is obviously insufficient.

[0140] Table 2: Physical performance comparison test

[0141] Test items Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Color fastness (grade) 4.3 3.5 4.1 4.0 Friction fastness (grade) 4.1 3.0 3.8 3.6 Interface bonding strength (N / cm) 28.5 24.2 26.1 25.3 Breaking strength (N) 245 198 231 218 Elongation at break (%) 18.2 15.7 17.3 16.8

[0142] In the color fastness test, according to GB / T3921.1-2008 standard, 5 parallel samples were taken from each group of fiber samples; the samples were combined with the lining and placed in a xenon lamp weathering test chamber with a light intensity of 550W / m 2 , temperature 35±3℃; exposure time continuous irradiation 35 hours; use standard gray card to compare the color change of the sample before and after exposure, and evaluate the color fastness grade.

[0143] In the rubbing fastness test, according to GB / T3920-2008 standard, the sample is fixed on the rubbing fastness meter and rubbed back and forth 10 times with a standard white cotton cloth under a pressure of 10N. The white cotton cloth is moistened with distilled water to a moisture content of 65%, and the rubbing procedure is repeated. The degree of staining of the white cotton cloth is assessed with a gray card, and the dry and wet rubbing fastness grades are recorded.

[0144] In the interface bonding strength test, the maximum tensile force when the fibers begin to separate is recorded and the bonding strength per unit width is calculated.

[0145] In the breaking strength test, according to GB / T3916-2013 standard, the test length is 500mm, the pre-tension is 0.5cN / dtex, the tensile speed is 500mm / min, 50 samples are tested, and the average value is taken as the breaking strength.

[0146] In the elongation at break test, elongation at break (%) = (gauge length at break - initial gauge length) / initial gauge length × 100%.

[0147] Example 2 achieved a color fastness rating of 4.3, significantly outperforming all comparative examples. This is primarily due to multiple color stabilization mechanisms: through the covalent bonding of natural plant dyes with modified chitosan: through dual modification by thiolation and imidazolylation, the active groups on the chitosan molecular chain form stable covalent bonds with polyphenolic compounds found in betel nut tannins and madder, rather than simple physical adsorption. This molecular-level bonding significantly improves the dye's fixation rate. The coordination complex formed by hydroxysafflor yellow A and titanium ions exhibits enhanced photostability and is resistant to photolysis and fading under ultraviolet light, a unique advantage unattainable by traditional chemical dyes. The 35:22:20 fiber ratio allows the natural antioxidant properties of cotton fiber, the UV shielding effect of nylon, and the chemical stability of polyester to synergistically protect the dye's color stability. Comparative Example 1, using a formula with equal weight ratios, fails to achieve this synergistic protective effect. The excessively high proportion of nylon reduces overall softness and affects dye distribution uniformity. Although the proportions of Comparative Examples 2 and 3 are reasonable, they lack the covalent color-fixing mechanism of modified chitosan, and their color fastnesses are only 4.1 and 4.0, respectively.

[0148] The friction fastness of Example 2 reached level 4.1, demonstrating the dual effects of interface enhancement and surface optimization. The interpenetrating network structure formed by the titanate coupling agent BY-T6102 and the zirconium-aluminum coupling agent TMC-101 in a ratio of 1:0.5 forms a dense protective layer on the fiber surface. The attapulgite clay, calcined at 750°C and modified with octadecanoic acid, forms a nanoscale reinforcement phase on the fiber surface. The long chain structure of octadecanoic acid provides excellent lubricity, reducing surface damage during friction. The equal weight ratio formulation in Comparative Example 1 resulted in uneven surface properties, with a friction fastness of only level 3.0. The unmodified attapulgite clay in Comparative Example 3 lacked surface lubricity, resulting in a friction fastness of only level 3.6.

[0149] The interface bonding strength of Example 2 reaches 28.5N / cm, which is 9.2% higher than the best comparative example; the coupling agent forms a uniform modified layer on the fiber surface. The titanate coupling agent reacts with the amino group at the end of the nylon molecular chain, and the zirconium aluminum coupling agent reacts with the hydroxyl group of the polyester molecular chain to form a strong chemical bonding interface. The thiol group in the thiolated chitosan forms a coordination bond with the metal ion, and the imidazole group forms a hydrogen bond with the polar group on the fiber surface, which plays a molecular bridging role and significantly enhances the bonding force between fibers. The ratio of 35:22:20 achieves the best match of different fiber moduli. Cotton fiber provides flexibility, nylon provides elasticity, and polyester fiber provides rigidity, forming a gradient modulus structure to avoid stress concentration. The 33.3:33.3:33.3 ratio of comparative example 1 destroys this mechanical matching, and the interface bonding strength is only 24.2N / cm, a decrease of 15%.

[0150] The breaking strength of Example 2 reaches 245N, which is better than all the comparative examples. The precise fiber ratio enables the load to be efficiently transferred between the three fibers. When the cotton fiber reaches the yield point first, the load is transferred to the nylon fiber through the interface, and finally the high-strength polyester fiber bears the main load. Silver, copper, and zinc ions form a nano-scale dispersed phase in the fiber, which plays a role in dispersion strengthening. In particular, the coordination effect of zinc ions and polyester molecular chains increases the interaction force between molecular chains; the crosslinking agent forms a three-dimensional crosslinked network between the fibers, connecting the discrete fiber bundles into a whole, and significantly improving the overall strength of the composite system.

[0151] Example 2 maintained a reasonable elongation of 18.2%, improving strength while maintaining good flexibility. The different elongation properties of the three fibers, when combined, enabled synergistic deformation, avoiding brittle fracture. The long-chain structure of seaweed polysaccharides acted as a stress buffer during deformation, improving the material's toughness.

[0152] Table 3: Carrier performance comparison

[0153] Test indicators Example 2 (Modified Attapulgite) Comparative Example 3 (unmodified attapulgite) <![CDATA[Specific surface area (m 2 / g)]]> 285 178 Specific surface area increase rate 60.1% Baseline value Ion exchange capacity (mmol / 100g) 42.3 26.8 Organic phase dispersibility score 9.2 / 10 4.1 / 10 Controlled release stability coefficient 0.92 0.64 Loading ion retention rate (after 30 washes) 85.7% 60.3%

[0154] In the specific surface area test, the BET method was used. Modified attapulgite and unmodified attapulgite were degassed in a vacuum drying oven at 120°C for 6 hours to remove moisture and impurities adsorbed on the surface. A specific surface area analyzer was used with nitrogen as the adsorbent to measure the adsorption isotherm at liquid nitrogen temperature. The specific surface area was calculated using the BET equation.

[0155] In the ion exchange capacity test, the dried attapulgite sample was accurately weighed; the sample was soaked in ammonium acetate solution for 24 hours, shaking 6 times during the period to ensure sufficient exchange; the sample was washed with ethanol until no chloride ions were detected in the washing solution; the adsorbed NH 4+ , collect the replacement fluid; determine the replaced nitrogen content using the Kjeldahl method and calculate the ion exchange capacity.

[0156] In the evaluation of organic phase dispersibility, the sample was added to toluene and ultrasonically dispersed for 30 minutes; the sample was allowed to stand at room temperature for 24 hours, and the dispersion state was observed every 2 hours; the particle size distribution of the particles in the dispersion was measured using a laser particle size analyzer; and a comprehensive score was calculated based on the sedimentation velocity, dispersion uniformity, and particle size distribution.

[0157] In the controlled-release stability coefficient test, the sample was immersed in a CuCl2 solution, copper ions were loaded according to the conditions of Example 2, and a dynamic release test was performed in artificial sweat. Samples were taken and tested at regular intervals. The controlled-release stability coefficient = linear release time period / total test time.

[0158] In the loaded ion retention rate test, 30 washing cycles were performed in accordance with GB / T8629-2017 standard, and the retention rate (%) = (content after washing / content before washing) × 100%.

[0159] Significantly increased surface area (285m² / g vs 178m² / g, a 60.1% increase)

[0160] The specific surface area of ​​the modified attapulgite in Example 2 reached 285m 2 / g, 178m 2 / g increased by 60.1%. This is because during the high temperature calcination of attapulgite at 750℃, the hydroxyl groups in the structure undergo dehydration condensation reaction. This process not only removes interlayer water and surface adsorbed water, but more importantly, forms a large number of micropores and mesopores in the crystal structure. High temperature treatment leads to the formation of some Al 3+ and Si 4+ Ions overflow from the crystal lattice, forming point and line defects. These defective areas have higher surface activity and a larger specific surface area. The steam pressure generated during calcination partially peels off the layered structure of the attapulgite, exposing more internal surface areas and directly contributing to the increase in specific surface area.

[0161] The ion exchange capacity of the modified attapulgite reached 42.3 mmol / 100 g, which was 57.8% higher than that of the unmodified attapulgite (26.8 mmol / 100 g). This was because the rapid cooling process after high-temperature calcination formed more surface defect sites, which reacted with H during the subsequent acid treatment. + Combined to form surface hydroxyl groups. Treatment with 6-10% dilute hydrochloric acid further increases the surface hydroxyl density, providing more active sites for ion exchange. + Ions enter the interlayers of attapulgite and partially replace the original cations. At the same time, the interlayer spacing expands from the original approximately 1.2nm to 1.5-1.8nm, providing more space for the entry of large ions.

[0162] The organic phase dispersibility score for Example 2 reached 9.2, while that for Comparative Example 3 was only 4.1. The octadecanoic acid molecular chains form a "brush" structure on the surface, providing steric hindrance and preventing particle aggregation. This structure is particularly stable in organic solvents, ensuring good dispersibility. The hydrophobic surface has good compatibility with organic solvents such as toluene, reducing interfacial free energy and making the particles more easily wetted and dispersed by the organic phase. The unmodified attapulgite has a highly hydrophilic surface and easily aggregates and settles in the organic phase.

[0163] The controlled-release stability coefficient of Example 2 reached 0.92, far superior to 0.64 in Comparative Example 3, indicating that an ideal controlled-release effect with near-zero-order kinetics was achieved: the octadecanoic acid-modified layer formed a hydrophobic controlled-release membrane on the surface of the attapulgite. Ions must first pass through this hydrophobic membrane before entering the aqueous phase. This mass transfer process becomes the controlling step, keeping the release rate relatively constant. The modified attapulgite formed regular ion transport channels with relatively uniform diameter and length, ensuring stable mass transfer resistance and release rate.

[0164] The copper ion retention rate of Example 2 reached 85.7%, which was 42% higher than the 60.3% of Comparative Example 3, reflecting the synergistic effect of multiple fixation mechanisms: copper ions formed chemical coordination bonds -Si-OH+Cu with the hydroxyl groups on the surface of the modified attapulgite. 2+ →-Si-O-Cu + +H + This chemical bonding is more stable than physical adsorption and is not easily destroyed by detergents. The hydrophobic surface layer formed by octadecanoic acid plays a protective role during the washing process, preventing detergent molecules from penetrating deeply into the carrier and reducing ion loss. The microporous structure formed by high-temperature calcination provides a "safe haven" for copper ions. Even under strong mechanical agitation and chemical washing conditions, the ions deep inside the pores remain stable.

[0165] Example 4

[0166] A method for preparing antibacterial and environmentally friendly dyed fibers comprises the following steps:

[0167] preparing titanium-containing silicone oil emulsion, coupling agent mixture, and antibacterial and mildew-proof finishing agent;

[0168] The titanium-containing silicone oil emulsion was evenly sprayed on the surface of the cotton fiber, with the spraying amount being 10% of the weight of the cotton fiber, and treated at 70°C for 45 minutes to obtain modified cotton fiber;

[0169] The coupling agent mixture was sprayed on the surface of the nylon fiber in an atomized manner, with the spraying amount being 6% of the weight of the nylon fiber, and treated at 60°C for 30 minutes to obtain modified nylon fiber;

[0170] The antibacterial and mildew proof finishing agent is sprayed on the surface of the polyester fiber in an amount of 15% of the weight of the polyester fiber, and treated at 100°C for 50 minutes to obtain a modified polyester fiber;

[0171] The modified cotton fibers were dispersed in a silver nitrate solution, shaken and dispersed at 85°C for 7 hours, filtered and dried to complete the silver ion loading;

[0172] The modified attapulgite was placed in a copper chloride solution, shaken and dispersed at 70°C for 3 hours, filtered and dried to complete the copper ion loading;

[0173] Immerse zeolite powder in zinc sulfate solution at a weight ratio of 1:4, let it stand for 3 hours, then filter and dry to complete the zinc ion loading;

[0174] Modified cotton fiber, modified nylon fiber and modified polyester fiber loaded with silver ions were weighed and mixed with functional additives. Antibacterial and environmentally friendly dyed fibers were prepared through opening, mixing, carding, drawing, woolen spinning and worsted spinning processes.

[0175] The concentration of silver nitrate solution is 0.3 mol / L, the concentration of copper chloride solution is 0.1 mol / L, and the concentration of zinc sulfate solution is 0.2 mol / L.

[0176] What you need to know is that the opening process includes the following steps:

[0177] Feed various fiber raw materials into the opening machine, set the opening roller speed to 400r / min; the fiber bundles are decomposed into single fibers by the action of the needle cloth, and impurities and short fibers are removed; the opening degree is controlled at 85-90% to ensure that the fibers are fully separated without damaging the fiber length; the fiber length after opening is kept within the range of 25-28mm.

[0178] The mixing process includes the steps of:

[0179] The various fibers after opening are put into the mixer in proportion; the air flow mixing method is adopted, and the air flow speed is controlled at 12-15m / s; the mixing time is 15 minutes to ensure that the components are evenly distributed; at the same time, functional additives are added and evenly dispersed by spraying.

[0180] The carding process includes the following steps:

[0181] The mixed fibers are fed into the carding machine with the main combing roller rotating at 180r / min and the doffer roller rotating at 15r / min. The fibers are further separated and arranged into parallel shapes by the combing action of the card cloth. Short fibers and impurities are removed during the carding process. A continuous fiber web is output with a thickness controlled at 2-3mm.

[0182] The drawing process includes the following steps:

[0183] 6-8 carded fiber webs are combined and fed into the drawing frame; the fibers are further parallelized and straightened through the drawing action, and the drawing ratio is set to 6-8 times; the front roller speed of the drawing frame is 120r / min, and the rear roller speed is 15r / min; the linear density of the output fiber strip is controlled at 4-5ktex, and the strip uniformity CV value is <3%.

[0184] The roving process includes the following steps:

[0185] The drawn fiber strips are fed into the roving frame for preliminary twist spinning; the drafting ratio is set to 8-10 times, and the spindle speed is 800-1000r / min; the twist coefficient is controlled at 90-110 to form a roving with a certain strength; the roving linear density is controlled at 500-600tex, and the strength is ≥80cN.

[0186] The worsted spinning process includes the following steps:

[0187] The roving is fed into a ring spinning machine for final spinning; the drafting ratio is set to 15-20 times, the spindle speed is 12,000-15,000 r / min; the twist coefficient is controlled at 110-130 to form the final antibacterial and environmentally friendly dyed fiber; the yarn density is controlled at 30-40 tex, the breaking strength is ≥180 cN, and the elongation at break is 16-20%.

[0188] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, and all of these should be included in the scope of the present invention.

Claims

1. An antibacterial and environmentally friendly dyed fiber, characterized by: The composite fiber system comprises modified cotton fiber, modified nylon fiber and modified polyester fiber, wherein the mass ratio of the modified cotton fiber, the modified nylon fiber and the modified polyester fiber is 30-40:20-25:15-25; The antibacterial and environmentally friendly dyed fiber also includes silver ions, copper ions, and zinc ions; The composite fiber system further comprises the following functional additives in parts by weight: Modified chitosan: 6-8 parts; Modified attapulgite: 5-8 parts; Natural plant dyes: 3-5 parts; Zeolite powder: 1-3 parts; Seaweed polysaccharide: 1-2 parts; Cross-linking agent: 5-7 parts; Wherein, when the silver ions, copper ions, and zinc ions are prepared, the method includes: Disperse the modified cotton fiber in a silver nitrate solution, shake and disperse at 80-85°C for 5-10 hours, filter and dry to complete the silver ion loading; The modified attapulgite was placed in a copper chloride solution, shaken and dispersed at 65-70°C for 2-4 hours, filtered and dried to complete the copper ion loading; Soak the zeolite powder in zinc sulfate solution at a weight ratio of 1:4-6, let it stand for 2-3 hours, then filter and dry to complete the zinc ion loading; The modified cotton fiber is prepared by impregnation with titanium-containing silicone oil emulsion and then drying; The modified nylon fiber is prepared by treating a coupling agent mixture and then drying the mixture; The modified polyester fiber is prepared after pretreatment with an antibacterial and mildew-proof finishing agent; The titanium-containing silicone oil emulsion is prepared according to the following method: Add 3-5 parts of Span 60 to 30-50 parts of dichloromethane according to weight; At 40°C, add 1-2 parts of butyl titanate and 1-2 parts of composite silicone oil while stirring, then add 0.5-2 parts of silane coupling agent KH560 and 0.5-2 parts of emulsifier N in sequence, and then stir evenly; Then add 60 to 100 parts of water, continue stirring at 40°C for 40 minutes, then heat to 60°C and stir thoroughly to obtain a titanium-containing silicone oil emulsion; Wherein, the composite silicone oil is a mixture of alkyl-modified silicone oil and polyether-modified silicone oil, and the weight ratio of alkyl-modified silicone oil to polyether-modified silicone oil is 1:0.5-2; The composite silicone oil also includes hydroxy safflower yellow pigment A, and the ratio of the composite silicone oil to the hydroxy safflower yellow pigment A is 10:1-3; The preparation method of the modified attapulgite comprises: Calcine the basic attapulgite at 700-800℃ for 1-2h and grind it into 80-100 mesh particles; Then add 6-10% mass fraction of dilute hydrochloric acid, the weight ratio of basic attapulgite to dilute hydrochloric acid is 1:3-5, stir at 65-75℃ for 1-2h, filter and wash, dry, and re-grind into 60-80 mesh particles; Then, the modified attapulgite is immersed in a solution of octadecanoic acid and ethanol in a weight ratio of 1:20-30, stirred at 85-110° C. for 3-5 hours, filtered and washed, and then dried at 50-60° C. to obtain the modified attapulgite.

2. The antibacterial and environmentally friendly dyed fiber according to claim 1, characterized in that: The preparation method of the alkyl modified silicone oil is: Mix isododecane and dimethyl silicone oil in a weight ratio of 2:1 to 1.5; After stirring evenly, add potassium hydroxide in an amount of 0.01 to 0.02 times the weight of isododecane to carry out a catalytic reaction, raise the temperature to 100 to 150° C., and continue the reaction until the system becomes a solid-liquid mixture; Then the temperature is lowered to 10-20° C., filtered, washed with water until neutral, and then dried to obtain alkyl-modified silicone oil.

3. The antibacterial and environmentally friendly dyed fiber according to claim 2, characterized in that: The coupling agent mixture is prepared according to the following method: Add 1g of coupling agent to 10ml of citric acid solution and mix with a citric acid solution with a concentration of 0.04-0.25g / L; Then, ethanol was added and stirred to obtain a coupling agent mixture; The ratio of the citric acid solution to ethanol is 100:2-5; The coupling agent is a composite system of a titanate coupling agent and a zirconium-aluminum coupling agent; The titanate coupling agent is selected from Y-570 or BY-T6102, the zirconium-aluminum coupling agent is selected from TMC-101 or TMC-102, and the weight ratio of the titanate coupling agent to the zirconium-aluminum coupling agent is 1:0.3-0.

8.

4. The antibacterial and environmentally friendly dyed fiber according to claim 3, characterized in that: The antibacterial and mildew-proof finishing agent is composed of a basic polymer component and a functional polymer component; The base polymer component includes: 10 parts of methyl methacrylate, 8 parts of acrylic acid, 1.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2.5 parts of zinc methacrylate, 1.2 parts of 2,4-dimethoxyphenol, and 1.5 parts of an azo initiator, and is dispersed in 100 parts of ethyl acetate; The functional polymer component includes: 18 parts of tricyanoglyceryl ether propyl trimethoxysilane, 2-4 parts of nano titanium dioxide, and 0.5-1 parts of penetration enhancer. The penetration enhancer is an ammonia solution with a concentration of 20-25%.

5. The antibacterial and environmentally friendly dyed fiber according to claim 4, characterized in that: The modified chitosan is chitosan that is double-modified by thiolation and imidazoleization, and the preparation method thereof comprises: Dissolve the basic chitosan in a hydrochloric acid solution, add sodium periodate oxidant, stir at a speed of 100-200 r / min, and obtain the mercapto-containing chitosan by filtering; In a reaction vessel, add mercaptochitosan and anhydrous butanol, stir, then add polyethylene glycol diglycidyl ether, maintain the temperature at 50-55°C, react for 1-2 hours, filter under reduced pressure, wash and dry to obtain an intermediate; Anhydrous butanol was added to the reaction vessel, and after stirring evenly at 10-15°C, sodium cyanoborohydride reducing agent was slowly added. After reacting for 1-2 hours, the modified chitin was obtained by filtration under reduced pressure; 2-Mercaptoimidazole is added to a 0.2-0.3 mol / L hydrochloric acid solution, and the modified chitin is added after stirring. After reacting for 15-20 hours, the modified chitosan is obtained, and the molecular weight is 55,000-70,000.

6. A method for preparing the antibacterial and environmentally friendly dyed fiber according to any one of claims 1 to 5, characterized in that: The following steps are included: preparing titanium-containing silicone oil emulsion, coupling agent mixture, and antibacterial and mildew-proof finishing agent; The titanium-containing silicone oil emulsion is evenly sprayed on the surface of the cotton fiber, with the spraying amount being 8-12% of the weight of the cotton fiber, and treated at 60-80°C for 30-45 minutes to obtain modified cotton fiber; The coupling agent mixture is sprayed on the surface of the nylon fiber in an atomized manner, with the spraying amount being 5-8% of the weight of the nylon fiber, and treated at 50-70°C for 20-30 minutes to obtain the modified nylon fiber; The antibacterial and mildew proof finishing agent is sprayed on the surface of the polyester fiber in an amount of 10-15% of the weight of the polyester fiber, and treated at 80-100° C. for 40-60 minutes to obtain a modified polyester fiber; Disperse the modified cotton fiber in a silver nitrate solution, shake and disperse at 80-85°C for 5-10 hours, filter and dry to complete the silver ion loading; The modified attapulgite was placed in a copper chloride solution, shaken and dispersed at 65-70°C for 2-4 hours, filtered and dried to complete the copper ion loading; Soak the zeolite powder in zinc sulfate solution at a weight ratio of 1:4-6, let it stand for 2-3 hours, then filter and dry to complete the zinc ion loading; Modified cotton fiber, modified nylon fiber and modified polyester fiber loaded with silver ions were weighed and mixed with functional additives. Antibacterial and environmentally friendly dyed fibers were prepared through opening, mixing, carding, drawing, woolen spinning and worsted spinning processes.

7. The method for preparing the antibacterial and environmentally friendly dyed fiber according to claim 6, characterized in that: The concentration of the silver nitrate solution is 0.1-0.5 mol / L, the concentration of the copper chloride solution is 0.05-0.2 mol / L, and the concentration of the zinc sulfate solution is 0.1-0.3 mol / L.