Natural bacteriostatic core linen yarn and preparation method thereof
By wrapping modified flax fibers with polyester filaments and using composite finishing liquid and complexing finishing technology, the problems of insufficient antibacterial effect and softness of flax yarn have been solved, resulting in a highly efficient and multifunctional natural antibacterial core flax yarn.
Patent Information
- Application Number
- CN202511823859.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-05
- Publication Date
- 2026-01-27
AI Technical Summary
While pursuing a dry and crisp style, existing linen yarns have unsustainable antibacterial effects and insufficient softness, making it difficult to meet the multifunctional needs of high-end close-fitting textiles, especially in terms of the molecular functionalization design within the fiber.
By wrapping modified flax fibers with polyester filaments, polyaniline-grafted sodium lignosulfonate was prepared by polymerizing amine-functionalized sodium lignosulfonate with aniline. Subsequently, it was reacted with a phytic acid mixed solution to form a composite finishing solution, which was then microwave baked and subjected to carboxybetaine methacrylate grafting and copper chloride complexation finishing to construct a multidentate ligand complex structure.
It achieves long-lasting and highly effective antibacterial function of yarn, improves antistatic, anti-UV and flame retardant properties, and improves the softness and structural stability of yarn, meeting the multifunctional needs of high-end textiles.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of textile materials technology, specifically to a natural antibacterial core linen yarn and its preparation method. Background Technology
[0002] Flax fiber, as a natural cellulose fiber, is widely used in the textile industry due to its excellent moisture absorption, breathability, crispness, and biodegradability. Although flax itself has good natural antibacterial potential, its antibacterial effect is usually weak and not durable, making it difficult to meet the market demand for high-performance, long-lasting antibacterial textiles. At the same time, its low fiber elongation, insufficient softness, and tendency to pill also limit its application in high-end intimate apparel. Traditional flax yarns, while pursuing a dry and crisp style, often compromise on feel and skin-friendliness. Its functional improvements largely rely on surface finishing techniques, generally resulting in limited functionality and insufficient durability.
[0003] In recent years, wrapped yarn technology has received widespread attention in order to balance the unique style and comprehensive performance of linen products. This technology involves wrapping short linen fiber yarns with filaments, which can effectively improve the strength and abrasion resistance of the yarn and enhance its processing performance. However, existing linen wrapped yarn technologies mainly focus on harmonizing physical properties and hand feel, and still have significant shortcomings in endowing the yarn with durable, efficient, and stable multifunctionality, especially in antibacterial properties. Therefore, there is an urgent need for a new technological approach that combines the natural characteristics of linen fibers, the structural advantages of wrapped yarn, and molecular functionalization design that penetrates deep into the fiber to develop high-performance natural antibacterial core linen yarn that integrates comfort, durability, and long-lasting multifunctionality. Summary of the Invention
[0004] The purpose of this invention is to provide a natural antibacterial core hemp yarn and its preparation method, so as to solve the problems existing in the prior art.
[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A natural antibacterial core linen yarn, wherein the natural antibacterial core linen yarn is made by wrapping and clamping polyester filaments with modified flax fiber roving and then finishing.
[0006] As an optimization, the modified flax fiber is obtained by pretreating flax fiber with alkali, immersing it in a composite finishing solution, and then microwaving and baking it.
[0007] As an optimization, the composite finishing solution is prepared by reacting sodium lignosulfonate with p-phenylenediamine and formaldehyde to obtain amine-functionalized sodium lignosulfonate, then polymerizing it with aniline to obtain polyaniline-grafted sodium lignosulfonate, and finally reacting it with a mixed solution of phytic acid.
[0008] As an optimization, the post-treatment includes sequential grafting of carboxybetaine methacrylate and complexation with copper chloride.
[0009] A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:(0.5~0.8):(2~2.5):(4~5). Mix sodium lignosulfonate with deionized water and stir at 25~30℃ and 200~400r / min until dissolved. Adjust the pH to 10~12 with 1M sodium hydroxide solution. Add p-phenylenediamine and continue stirring for 10~20min. Add 10wt% formaldehyde solution, heat to 65~75℃ and continue stirring for 4~6h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate. 1:(1.8~2.2):(2.5~3):(90~110) Weigh out sodium amine-functionalized lignin sulfonate, aniline, sodium persulfate and deionized water. Mix sodium amine-functionalized lignin sulfonate with deionized water and stir at 0~5℃ and 200~400r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 10~20min. Add concentrated sulfuric acid dropwise to stabilize the pH at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 6~8h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignin sulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamine at a mass ratio of 1:(0.05~0.08):(0.1~0.15); disperse 10wt% of polyaniline-grafted lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 25~30℃ and 200~400r / min for 22~26h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 10~20m. The composite finishing solution was obtained by soaking flax fibers in a 14wt% sodium hydroxide solution for swelling pretreatment for 22-26 hours, and washing them with water until neutral to obtain pretreated flax fibers. The pretreated flax fibers were then immersed in the composite finishing solution at a solid-liquid ratio of 1:13-16, stirred at 85-95℃ and 200-400r / min for 3-5 hours, removed and placed in a microwave oven for 3-5 minutes, and then baked at 120-130℃ for 5-7 minutes to obtain modified flax fibers. (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn is immersed in acetone solution, ultrasonically treated for 2-3 hours, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn is immersed in acetone solution of 0.5-0.7 mol / L benzophenone for 25-35 minutes, taken out and dried, then immersed in 0.5-2 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 25-30 minutes, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn is immersed in 3-5 wt% anhydrous copper chloride aqueous solution, treated at 25-35℃ for 4-6 hours, and air-dried to obtain natural antibacterial core-linen yarn.
[0010] As an optimization, the flax fiber in step (2) has an average length of 30 mm and a fiber fineness of about 4.2 dtex, and was purchased from Haiyan Jinyi Silk Textile Co., Ltd.
[0011] As an optimization, the reaction process of the polyaniline-grafted sodium lignin sulfonate in step (1) and the modified flax fiber in step (2) is as follows:
[0012] As an optimization, the polyester filament yarn in step (3) has a linear density of 8.33 tex and is manufactured by Jiangsu Kangyichen Life Technology Co., Ltd.
[0013] As an optimization, the main process parameters for the opening, carding, drawing, and roving processes in step (3) are as follows: ① Cleaning process: The speed of the cotton grabber is 730 r / min, the distance of the blade extending out of the rib is 1.5 mm, and the downward stroke is 2 mm / time; ② Carding process: cylinder speed 330r / min, licker-in speed 480r / min, licker-in and feed plate distance 0.35mm, cylinder and flats distance 0.25 / 0.23 / 0.20 / 0.23mm, sliver weight 18.5g / 5m; ③Drawing process: First draw: 8 strands are combined, weight 22.5g / 5m, total draft 8.65 times, back zone draft 1.65 times; Second draw: 6 strands are combined, weight 18.5g / 5m, total draft 8.35 times, back zone draft 1.15 times; ④ Roving process: Roving weight 8.6g / 10m, twist 5.71 twists / 10m, total draft 7.97 times, back zone draft 1.15 times.
[0014] As an optimization, when the polyester filament and the drawn roving are twisted after being output by the front roller in step (3), the distance between the roving sliver and the polyester filament is 4mm, the roller spacing is 17mm*38mm, and the twist coefficient is 375.
[0015] As an optimization, the polyester filament draw ratio in step (3) is 1.03 times, and the total draw ratio of the roving is 25.08.
[0016] As an optimization, the ultraviolet irradiation in step (3) uses an ultraviolet light source with a wavelength of 365nm and an irradiation intensity of 80~100mW / cm².
[0017] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing natural antibacterial core linen yarn, this invention first polymerizes amine-functionalized sodium lignin sulfonate with aniline to obtain polyaniline-grafted sodium lignin sulfonate, which is then reacted with a phytic acid mixed solution to obtain a composite finishing solution. After pretreatment, flax fibers are immersed in the composite finishing solution and then microwaved and baked to obtain modified flax fibers. The modified flax fibers are then processed through opening, carding, drawing, and roving to obtain roving, which is then combined with polyester filaments and twisted to obtain polyester core linen wrapped yarn. Finally, the polyester core linen wrapped yarn is treated with acetone, subjected to free radical grafting with carboxybetaine methacrylate aqueous solution, and complexed with copper chloride to obtain natural antibacterial core linen yarn.
[0018] First, in the fiber modification stage, amine-functionalized sodium lignosulfonate and aniline are polymerized under acidic conditions via ammonium persulfate initiation, grafting polyaniline conductive chains onto the lignin backbone to form a molecular conductive network that effectively dissipates charge, thereby endowing the fiber with durable antistatic properties. Simultaneously, the inherent carbonyl and phenolic hydroxyl structures of lignin, together with the conjugated system of polyaniline, constitute a highly efficient ultraviolet absorption layer, giving the final fabric excellent UV resistance. Subsequently, polyaniline-grafted sodium lignosulfonate reacts with a phytic acid mixed solution under a strongly alkaline environment. The phosphate groups in phytic acid react with the abundant hydroxyl groups in lignin and cellulose, promoting fiber cross-linking into char during high-temperature baking, forming a condensed phase flame-retardant barrier, significantly improving the material's flame-retardant properties.
[0019] Secondly, modified flax roving is wrapped with polyester filaments to form yarn, compensating for the poor softness of flax fibers while combining the mechanical properties of polyester filaments. In the yarn finishing stage, carboxybetaine methacrylate free radicals are grafted onto the surface of the polyester filaments through ultraviolet irradiation; the betaine structure itself provides contact antibacterial function. Subsequently, in the copper chloride complexation finishing process, the carboxyl groups on the carboxybetaine, the phosphate groups of phytic acid on the flax fiber surface, and the nitrogen atoms on the polyaniline chain act as multidentate ligands, forming a stable ternary complex structure with copper ions. This enhances the bonding force between the polyester filaments and flax fibers, strengthening the stability of the wrapping structure; it also constructs an antibacterial system that slowly releases copper ions, working synergistically with the betaine units to achieve highly efficient and durable broad-spectrum antibacterial function. Detailed Implementation
[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0021] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail. Example 1:
[0022] A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:0.5:2:4. Mix sodium lignosulfonate with deionized water and stir at 25℃ and 200r / min until dissolved. Adjust the pH to 10 with 1M sodium hydroxide solution, add p-phenylenediamine and continue stirring for 10min. Add 10wt% formaldehyde solution, heat to 65℃ and continue stirring for 4h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate; according to a mass ratio of 1:1 Weigh out amine-functionalized sodium lignosulfonate, aniline, sodium persulfate and deionized water. Mix the amine-functionalized sodium lignosulfonate with deionized water and stir at 0℃ and 200r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 10min. Add concentrated sulfuric acid dropwise until the pH stabilizes at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 6h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignosulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.05:0.1; Disperse 10wt% of polyaniline-grafted sodium lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 25℃ and 200r / min for 22h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 10min to obtain a composite finishing solution; Soak flax fibers in 14wt% sodium hydroxide solution for swelling pretreatment for 22h, wash with water until neutral to obtain pretreated flax fibers; Immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:13, stir at 85℃ and 200r / min for 3h, take them out and place them in a microwave oven for 3min, and bake at 120℃ for 5min to obtain modified flax fibers; (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 2 hours, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.5 mol / L benzophenone acetone solution for 25 minutes, taken out and dried, then immersed in 0.5 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 25 minutes, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn was immersed in 3 wt% anhydrous copper chloride aqueous solution, treated at 25℃ for 4 hours, and air-dried to obtain natural antibacterial core-linen yarn. Example 2:
[0023] A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:0.7:2.3:4.5. Mix sodium lignosulfonate with deionized water and stir at 27℃ and 300r / min until dissolved. Adjust the pH to 11 with 1M sodium hydroxide solution, add p-phenylenediamine and continue stirring for 15min. Add 10wt% formaldehyde solution, heat to 70℃ and continue stirring for 5h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate; weigh sodium lignosulfonate according to a mass ratio of 1:0.7:2.3:4.5. Weigh out amine-functionalized sodium lignosulfonate, aniline, sodium persulfate and deionized water. Mix the amine-functionalized sodium lignosulfonate with deionized water and stir at 3℃ and 300r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 15min. Add concentrated sulfuric acid dropwise until the pH stabilizes at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 7h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignosulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.07:0.13; Disperse 10wt% of polyaniline-grafted sodium lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 27℃ and 300r / min for 24h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 15min to obtain a composite finishing solution; Soak flax fibers in a 14wt% sodium hydroxide solution for swelling pretreatment for 24h, wash with water until neutral to obtain pretreated flax fibers; Immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:15, stir at 90℃ and 300r / min for 4h, take them out and place them in a microwave oven for 4min, and bake at 125℃ for 6min to obtain modified flax fibers; (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 2.5 h, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.6 mol / L benzophenone acetone solution for 30 min, taken out and dried, then immersed in 1 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 27 min, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn was immersed in 4 wt% anhydrous copper chloride aqueous solution, treated at 30℃ for 5 h, and air-dried to obtain natural antibacterial core-linen yarn. Example 3:
[0024] A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:0.8:2.5:5. Mix sodium lignosulfonate with deionized water and stir at 30℃ and 400r / min until dissolved. Adjust the pH to 12 with 1M sodium hydroxide solution, add p-phenylenediamine and continue stirring for 20min. Add 10wt% formaldehyde solution, heat to 75℃ and continue stirring for 6h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate; according to a mass ratio of 1: 2.2:3:110 Weigh out sodium amine-functionalized lignin sulfonate, aniline, sodium persulfate and deionized water. Mix sodium amine-functionalized lignin sulfonate with deionized water and stir at 5℃ and 400r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 20min. Add concentrated sulfuric acid dropwise until the pH stabilizes at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 8h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignin sulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.08:0.15; disperse 10wt% of polyaniline-grafted sodium lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 30℃ and 400r / min for 26h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 20min to obtain a composite finishing solution; soak flax fibers in 14wt% sodium hydroxide solution for swelling pretreatment for 26h, wash with water until neutral to obtain pretreated flax fibers; immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:16, stir at 95℃ and 400r / min for 5h, take them out and place them in a microwave oven for 5min, and bake at 130℃ for 7min to obtain modified flax fibers; (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 3 hours, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.7 mol / L benzophenone acetone solution for 35 minutes, taken out and dried, then immersed in 2 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 30 minutes, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn was immersed in 5 wt% anhydrous copper chloride aqueous solution, treated at 35℃ for 6 hours, and air-dried to obtain natural antibacterial core-linen yarn.
[0025] Comparative Example 1: A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.07:0.13; Disperse sodium lignosulfonate at 10wt% in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 27℃ and 300r / min for 24h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 15min to obtain a composite finishing solution; Soak flax fibers in a 14wt% sodium hydroxide solution for swelling pretreatment for 24h, wash with water until neutral to obtain pretreated flax fibers; Immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:15, stir at 90℃ and 300r / min for 4h, take them out and place them in a microwave oven for 4min, and bake at 125℃ for 6min to obtain modified flax fibers; (2) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (3) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 2.5 h, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.6 mol / L benzophenone acetone solution for 30 min, taken out and dried, then immersed in 1 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 27 min, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn was immersed in 4 wt% anhydrous copper chloride aqueous solution, treated at 30℃ for 5 h, and air-dried to obtain natural antibacterial core-linen yarn.
[0026] Comparative Example 2: A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Flax fibers are sequentially processed through cleaning, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through a guide device, and the roving is drawn and merged with the two filaments in the front roller. After the two are output through the front roller, the polyester filaments wrap and hold the roving by twisting to obtain polyester core flax wrapped yarn. (2) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 2.5 h, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.6 mol / L benzophenone acetone solution for 30 min, taken out and dried, then immersed in 1 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 27 min, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn was immersed in 4 wt% anhydrous copper chloride aqueous solution, treated at 30℃ for 5 h, and air-dried to obtain natural antibacterial core-linen yarn.
[0027] Comparative Example 3: A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:0.7:2.3:4.5. Mix sodium lignosulfonate with deionized water and stir at 27℃ and 300r / min until dissolved. Adjust the pH to 11 with 1M sodium hydroxide solution, add p-phenylenediamine and continue stirring for 15min. Add 10wt% formaldehyde solution, heat to 70℃ and continue stirring for 5h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate; weigh sodium lignosulfonate according to a mass ratio of 1:0.7:2.3:4.5. Weigh out amine-functionalized sodium lignosulfonate, aniline, sodium persulfate and deionized water. Mix the amine-functionalized sodium lignosulfonate with deionized water and stir at 3℃ and 300r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 15min. Add concentrated sulfuric acid dropwise until the pH stabilizes at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 7h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignosulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.07:0.13; Disperse 10wt% of polyaniline-grafted sodium lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 27℃ and 300r / min for 24h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 15min to obtain a composite finishing solution; Soak flax fibers in a 14wt% sodium hydroxide solution for swelling pretreatment for 24h, wash with water until neutral to obtain pretreated flax fibers; Immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:15, stir at 90℃ and 300r / min for 4h, take them out and place them in a microwave oven for 4min, and bake at 125℃ for 6min to obtain modified flax fibers; (3) The modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; the roving is then stretched and twisted on a spinning machine to produce modified flax yarn. (4) The modified flax yarn was immersed in 4wt% anhydrous copper chloride aqueous solution, treated at 30℃ for 5h, and air-dried to obtain natural antibacterial flax yarn.
[0028] Comparative Example 4: A method for preparing a natural antibacterial core linen yarn includes the following preparation steps: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water according to a mass ratio of 1:0.7:2.3:4.5. Mix sodium lignosulfonate with deionized water and stir at 27℃ and 300r / min until dissolved. Adjust the pH to 11 with 1M sodium hydroxide solution, add p-phenylenediamine and continue stirring for 15min. Add 10wt% formaldehyde solution, heat to 70℃ and continue stirring for 5h. Precipitate with ethanol and dry to obtain amine-functionalized sodium lignosulfonate; weigh sodium lignosulfonate according to a mass ratio of 1:0.7:2.3:4.5. Weigh out amine-functionalized sodium lignosulfonate, aniline, sodium persulfate and deionized water. Mix the amine-functionalized sodium lignosulfonate with deionized water and stir at 3℃ and 300r / min until dissolved. Adjust the pH to 4 with concentrated sulfuric acid. Add aniline and continue stirring for 15min. Add concentrated sulfuric acid dropwise until the pH stabilizes at 4. Add 15wt% sodium persulfate aqueous solution dropwise and continue stirring for 7h. Collect the precipitate by vacuum filtration. Wash with water until the filtrate is neutral and dry to obtain polyaniline-grafted sodium lignosulfonate. (2) Prepare a phytic acid mixed solution by mixing 50wt% phytic acid aqueous solution, urea and dicyandiamide at a mass ratio of 1:0.07:0.13; Disperse 10wt% of polyaniline-grafted sodium lignin sulfonate in deionized water, adjust the pH to 12 with 1M sodium hydroxide, stir at 27℃ and 300r / min for 24h, add the phytic acid mixed solution at a volume ratio of 1:1, and continue stirring for 15min to obtain a composite finishing solution; Soak flax fibers in a 14wt% sodium hydroxide solution for swelling pretreatment for 24h, wash with water until neutral to obtain pretreated flax fibers; Immerse the pretreated flax fibers in the composite finishing solution at a solid-liquid ratio of 1:15, stir at 90℃ and 300r / min for 4h, take them out and place them in a microwave oven for 4min, and bake at 125℃ for 6min to obtain modified flax fibers; (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn was immersed in acetone solution, ultrasonically treated for 2.5 h, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn was immersed in 0.6 mol / L acetone solution of benzophenone for 30 min, taken out and dried, then immersed in 1 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 27 min, washed with boiling water, and dried to obtain natural antibacterial core-linen yarn.
[0029] Experimental Example 1: This example tests the properties of the natural antibacterial core linen yarns obtained in Examples 1-3 and Comparative Examples 1-4. The specific test items and methods are as follows: Antibacterial performance test method: The antibacterial properties of the natural antibacterial core linen yarns obtained in each example and the yarns of Comparative Examples 1-4 were tested according to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method". Escherichia coli and Staphylococcus aureus were used as bacterial strains, and the antibacterial rate was calculated.
[0030] Antibacterial rate = [(W t -Q t ) / W t ]×100% W t Q represents the colony count of a pure cotton sample, in CFU / mL; t The colony count is for the natural antibacterial core linen yarn sample, expressed in CFU / mL.
[0031] Flame retardant performance test method: The natural antibacterial core linen yarns obtained in each example and the yarns of comparative examples 1 to 4 were tested for limiting oxygen index values using a limiting oxygen index meter according to GB / T5454-1997 "Test for Burning Performance of Textiles - Oxygen Index Method".
[0032] Antistatic performance test method: The natural antibacterial core hemp yarns obtained in each example and the yarns of comparative examples 1 to 4 were tested for length resistivity using an XR-1A fiber resistivity tester. The voltage was 100V and the clamping distance was 10cm.
[0033] UV resistance test method: The natural antibacterial core linen yarn obtained in each example and the yarn of comparative examples 1 to 4 were woven into plain weave fabric with a warp and weft density of 360×320 threads / 10cm. According to GB / T18830-2002 "Evaluation of UV protection performance of textiles", the UV resistance performance of the fabric was tested using a textile UV resistance factor tester.
[0034] Yarn hairiness testing method: The natural antibacterial core linen yarns obtained in each example and the yarns of comparative examples 1-4 were tested for yarn hairiness using a YG172A yarn hairiness tester according to FZ / T01086-2020 "Textiles - Method for Determination of Yarn Hairiness - Projection Counting Method". A constant testing speed of 10 m / min was used, the segment length was 10 m, and each type of yarn was tested 20 times, and the average value was taken.
[0035] The results are shown in Table 1.
[0036] Table 1
[0037] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Table 1 reveals that the natural antibacterial core linen yarn prepared by this invention has good antibacterial properties, flame retardant properties, antistatic properties, and UV resistance.
[0038] A comparison of Examples 1-3 and Comparative Example 1 reveals that the introduction of polyaniline-grafted sodium lignosulfonate during flax fiber modification creates continuous conductive pathways on the fiber surface via polyaniline molecular chains. This effectively dissipates and neutralizes accumulated static charges, significantly improving the antistatic properties of the yarn. Simultaneously, the imine and amine nitrogen atoms abundant in the polyaniline molecular chains serve as effective metal ion coordination sites during subsequent copper chloride complexation, forming stable complex structures with copper ions. This not only enhances the loading and binding strength of antibacterial metal ions but also synergistically improves the yarn's durable and efficient antibacterial properties by disrupting bacterial cell membranes and interfering with their metabolic processes.
[0039] A comparison of Examples 1-3 and Comparative Example 2 reveals that the composite finishing solution used in the flax fiber modification process effectively improves antistatic properties by constructing a continuous conductive network on the fiber surface using polyaniline-grafted sodium lignin sulfonate, which effectively dissipates static charge. Simultaneously, the conjugated structure of polyaniline and the aromatic ring structure of lignin together form an ultraviolet absorption barrier, endowing the fiber with excellent UV resistance. Furthermore, the phosphate groups in phytic acid can catalyze the fiber to char at high temperatures, synergistically forming a dense char layer with polyaniline, significantly enhancing flame retardant properties. Moreover, the nitrogen atoms in the polyaniline molecule provide key coordination sites for subsequent copper ion complexation, greatly enhancing the loading and binding strength of metal ions, laying a solid foundation for obtaining durable antibacterial properties.
[0040] A comparison of Examples 1-3 and Comparative Example 3 reveals that the step of wrapping flax roving with polyester filament significantly improves the yarn structure. The tight wrapping of the flax fibers by the polyester filament effectively binds the ends of the short fibers, thereby significantly reducing yarn hairiness. Subsequently, carboxybetaine methacrylate is grafted onto the surface of the polyester component through ultraviolet irradiation. The betaine unit itself has contact antibacterial function, and the large number of carboxyl groups introduced together with the functional components on the surface of the flax fibers construct a multi-component coordination system, which greatly enhances the complexation capacity and stability of copper ions. Through the synergistic effect of the metal ion slow-release mechanism and contact sterilization, a dual-effect antibacterial effect is achieved.
[0041] By comparing Examples 1-3 and Comparative Example 4, it can be found that after treatment with anhydrous copper chloride aqueous solution, the copper ions form a stable multi-component coordination structure with the carboxyl groups in carboxylated betaine methacrylate grafted on the fiber surface, the phosphate groups in phytic acid on the flax fiber surface, and the nitrogen atoms on the polyaniline chain. This high-density complex network significantly increases the effective loading of active copper ions and their binding strength with the fiber. Copper ions significantly enhance the immediate antibacterial efficiency of the yarn through multiple pathways, such as continuously disrupting the integrity of bacterial cell membranes, interfering with intracellular enzyme systems, and promoting the generation of reactive oxygen species. At the same time, the established copper ion slow-release mechanism ensures long-term antibacterial performance, enabling the yarn to maintain excellent antibacterial effect even after multiple washes.
[0042] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.
Claims
1. A natural antibacterial core linen yarn, characterized in that, The natural antibacterial core linen yarn is made by wrapping and clamping polyester filaments with modified flax fiber roving and then finishing.
2. The natural antibacterial core linen yarn according to claim 1, characterized in that, The modified flax fiber is obtained by pretreating flax fiber with alkali, immersing it in a composite finishing solution, and then microwaving and baking it.
3. The natural antibacterial core linen yarn according to claim 2, characterized in that, The composite finishing solution is prepared by reacting sodium lignosulfonate with p-phenylenediamine and formaldehyde to obtain amine-functionalized sodium lignosulfonate, then polymerizing it with aniline to obtain polyaniline-grafted sodium lignosulfonate, and finally reacting it with a mixed solution of phytic acid.
4. The natural antibacterial core linen yarn according to claim 1, characterized in that, The post-treatment includes sequential grafting of carboxybetaine methacrylate and complexation with copper chloride.
5. A method for preparing a natural antibacterial core linen yarn, characterized in that, The preparation steps include the following: (1) Weigh sodium lignosulfonate, p-phenylenediamine, 10wt% formaldehyde solution and deionized water in a mass ratio of 1:(0.5~0.8):(2~2.5):(4~5). Dissolve sodium lignosulfonate in deionized water, add p-phenylenediamine and formaldehyde solution, and react at 65~75℃ to obtain amine-functionalized sodium lignosulfonate; Weigh sodium lignosulfonate, aniline, sodium persulfate and deionized water in a mass ratio of 1:(1.8~2.2):(2.5~3):(90~110). Dissolve sodium lignosulfonate in deionized water, add aniline and sodium persulfate aqueous solution, and react at 0~5℃ and pH=4 for 6~8h to obtain polyaniline-grafted sodium lignosulfonate. (2) Mix 50wt% phytic acid aqueous solution, urea and dicyandiamine at a mass ratio of 1:(0.05~0.08):(0.1~0.15) to prepare phytic acid mixed solution; disperse sodium polyaniline grafted lignin sulfonate in deionized water, adjust the pH to 12 with sodium hydroxide, add the phytic acid mixed solution after treatment to obtain composite finishing solution; Pretreated flax fibers were obtained by swelling and pre-treating them in sodium hydroxide solution for 22-26 hours. Pretreated flax fibers are immersed in a composite finishing solution and treated at 85-95℃ for 3-5 hours. After being removed, they are microwaved and baked to obtain modified flax fibers. (3) Modified flax fiber is processed through opening, carding, drawing and roving processes to obtain roving; two polyester filaments are introduced into the front roller through the guide device, the roving is drawn and merged with the two filaments in the front roller, and after the two are output through the front roller, the roving is wrapped and clamped by the polyester filaments through twisting to obtain polyester core flax wrapped yarn. (4) The polyester core-linen wrapped yarn is immersed in acetone solution, ultrasonically treated for 2-3 hours, and dried to obtain pretreated polyester core-linen wrapped yarn; the pretreated polyester core-linen wrapped yarn is immersed in acetone solution of 0.5-0.7 mol / L benzophenone for 25-35 minutes, taken out and dried, then immersed in 0.5-2 mol / L carboxybetaine methacrylate aqueous solution, irradiated with ultraviolet light in nitrogen atmosphere for 25-30 minutes, washed with boiling water, and dried to obtain modified polyester core-linen wrapped yarn; the modified polyester core-linen wrapped yarn is immersed in 3-5 wt% anhydrous copper chloride aqueous solution, treated at 25-35℃ for 4-6 hours, and air-dried to obtain natural antibacterial core-linen yarn.
6. The method for preparing a natural antibacterial core linen yarn according to claim 5, characterized in that, The average length of the flax fiber in step (2) is 30 mm, and the fiber fineness is about 4.2 dtex.
7. The method for preparing a natural antibacterial core linen yarn according to claim 5, characterized in that, The reaction process of the polyaniline-grafted sodium lignin sulfonate in step (1) and the modified flax fiber in step (2) is as follows:
8. The method for preparing a natural antibacterial core linen yarn according to claim 5, characterized in that, The polyester filament yarn in step (3) has a linear density of 8.33 tex.
9. The method for preparing a natural antibacterial core linen yarn according to claim 5, characterized in that, The polyester filament in step (3) has a draw ratio of 1.03 and a total roving draw ratio of 25.08.