An odor-resistant bio-based wool blended yarn and a method of making the same

Abstract

The application provides a deodorant bio-based wool blended yarn and a preparation method thereof, and belongs to the technical field of blended yarns; the application is prepared by modifying and assembling three bio-based materials; ion liquid is used to perform surface reconstruction on hemp fibers, so that the rigid surface of the hemp fibers is converted into a permanent soft and high-hygroscopic structure; a persistent antioxidant and deodorant nano coating is connected to the wool fibers through in-situ polymerization technology of tea polyphenols; a non-elution functional core filament is prepared by physically locking the antibacterial chitosan in the alginate network through wet spinning technology; the three are precisely combined through core spinning technology to form a synergistic core-shell structure; the shell is responsible for antioxidant from the source and creates a dry and antibacterial microenvironment, while the core actively kills bacteria and manages humidity, so that the coexistence of comfort, persistent functionality and sustainability is realized.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of blended yarns, and relates to an odor-resistant bio-based wool blended yarn and a preparation method thereof. BACKGROUND

[0002] Currently, there are still some problems in the development of high-performance bio-based blended yarns. First, there is an inherent contradiction between the comfort and performance of natural fibers. For example, hemp fiber is an ideal sustainable raw material with natural antibacterial and high moisture permeability, but its cellulose I crystal form leads to strong rigidity, rough touch, poor spinnability and other problems, which affects its application in high-end skin-friendly products. Traditional strong alkali or high-temperature cooking modification methods not only damage the fiber strength, but also produce a large amount of difficult-to-treat wastewater; and conventional biological enzyme treatment often has the problems of incomplete effect and high cost, which is difficult to fundamentally solve the comfort short board.

[0003] Secondly, the durability of the function is poor and there is an environmental safety hazard. The odor-resistant function of wool and other fibers is often finished through modification. However, mainstream finishing agents such as silver ions, copper ions and other heavy metal antibacterial agents have biological accumulation risks and potential ecological toxicity; quaternary ammonium salt antibacterial agents have the problem of poor washing fastness, and their function will decay with repeated washing. In addition, these functional finishes are usually single-acting, and if multiple functions such as ultraviolet resistance, oxidation resistance, etc. are to be achieved at the same time, multiple and complex chemical treatments are often required, which not only increases the production cost, but also goes against the original intention of green manufacturing. SUMMARY

[0004] In view of the above problems, the purpose of the present application is to provide an odor-resistant bio-based wool blended yarn and a preparation method thereof. The present application modifies and assembles three bio-based materials to prepare an odor-resistant bio-based wool blended yarn. First, the surface of hemp fiber is reconstructed using ionic liquid to convert its rigid surface into a permanently soft and high-hygroscopic structure; at the same time, a persistent antioxidant and odor-resistant nano-coating is attached to the wool fiber through in-situ polymerization of tea polyphenols; then, a non-eluting functional core filament is prepared by physically locking the antibacterial chitosan in the alginate network using wet spinning technology. Finally, the three are precisely combined by core spinning technology to form a synergistically enhanced core-shell structure: the shell is responsible for antioxidant from the source and creates a dry and antibacterial microenvironment, while the core actively kills bacteria and manages humidity, thereby realizing the coexistence of comfort, persistent functionality and sustainability.

[0005] To achieve this purpose, the present application adopts the following technical solutions:

[0006] In a first aspect, the present application provides a preparation method of an odor-resistant bio-based wool blended yarn, which comprises:

[0007] S1: hemp fibers are soaked in deionized water, dried to obtain pretreated hemp fibers; the pretreated hemp fibers are added into ionic liquid [Bmim]Cl and stirred to obtain reaction liquid A, the reaction liquid A is mixed with deionized water and stirred, and then filtered, washed and dried to obtain modified hemp fibers;

[0008] S2: a Tris-HCl solution is prepared, and a Tris-HCl buffer solution is obtained by adjusting the pH value; wool fibers are soaked in the Tris-HCl buffer solution to obtain reaction liquid B, and tea polyphenols are added to obtain reaction liquid C; after stirring and reaction, the reaction liquid C is filtered, washed and dried to obtain modified wool fibers;

[0009] S3: sodium alginate is put into deionized water, stirred and then left to stand to obtain a sodium alginate solution; chitosan is put into an acetic acid aqueous solution, stirred and then left to stand to obtain a chitosan solution; the chitosan solution is added into the sodium alginate solution, mixed uniformly, and vacuum degassed to obtain a mixed spinning dope; the mixed spinning dope is loaded into a syringe pump, and the obtained fine stream is pushed into a coagulation liquid to obtain a nascent fiber; the nascent fiber is first stretched in the coagulation liquid and then secondly stretched in water to obtain a pretreated composite filament; after washing, oiling and drying, a sodium alginate / chitosan composite filament is obtained;

[0010] S4: the modified hemp fibers and the modified wool fibers are mixed, opened, carded and drawn to obtain a fiber strip; the fiber strip and the sodium alginate / chitosan composite filament are spun into an odor-resistant bio-based wool blended yarn using a ring spinning device.

[0011] As a preferred technical solution of the present application, in step S1, the length of the hemp fibers is 30-50 mm, for example, can be 30 mm, 32 mm, 34 mm, 36 mm, 38 mm, 40 mm, 42 mm, 44 mm, 46 mm, 48 mm or 50 mm, but is not limited to the listed values, and other values not listed in this range are also applicable.

[0012] In some optional embodiments, the fineness of the hemp fibers is 5-15 dtex, for example, can be 5 dtex, 6 dtex, 7 dtex, 8 dtex, 9 dtex, 10 dtex, 11 dtex, 12 dtex, 13 dtex, 14 dtex or 15 dtex, but is not limited to the listed values, and other values not listed in this range are also applicable.

[0013] In some optional embodiments, the hemp fibers are soaked in deionized water at a temperature of 60-80 °C, for example, it can be 60 °C, 62 °C, 64 °C, 66 °C, 68 °C, 70 °C, 72 °C, 74 °C, 76 °C, 78 °C or 80 °C, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0014] In some optional embodiments, the hemp fibers are soaked in deionized water for a time of 0.5-1 h, for example, it can be 0.50 h, 0.55 h, 0.60 h, 0.65 h, 0.70 h, 0.75 h, 0.80 h, 0.85 h, 0.90 h, 0.95 h or 1.00 h, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0015] In some optional embodiments, the temperature for stirring the pretreated hemp fibers into the ionic liquid [Bmim]Cl is 90-110 °C, for example, it can be 90 °C, 92 °C, 94 °C, 96 °C, 98 °C, 100 °C, 102 °C, 104 °C, 106 °C, 108 °C or 110 °C, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0016] In some optional embodiments, the stirring speed for stirring the pretreated hemp fibers into the ionic liquid [Bmim]Cl is 100-200 rpm, for example, it can be 100 rpm, 110 rpm, 120 rpm, 130 rpm, 140 rpm, 150 rpm, 160 rpm, 170 rpm, 180 rpm, 190 rpm or 200 rpm, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0017] In some optional embodiments, the stirring time for stirring the pretreated hemp fibers into the ionic liquid [Bmim]Cl is 3-8 min, for example, it can be 3.0 min, 3.5 min, 4.0 min, 4.5 min, 5.0 min, 5.5 min, 6.0 min, 6.5 min, 7.0 min, 7.5 min or 8.0 min, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0018] In some optional embodiments, the mass ratio of the pretreated hemp fibers to the ionic liquid is 1:(20-50), for example, it can be 1:20, 1:23, 1:26, 1:29, 1:32, 1:35, 1:38, 1:41, 1:44, 1:47 or 1:50, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0019] In some optional embodiments, the volume ratio of the reaction solution A to deionized water is 1:(5-10), which can be 1:5.0, 1:5.5, 1:6.0, 1:6.5, 1:7.0, 1:7.5, 1:8.0, 1:8.5, 1:9.0, 1:9.5 or 1:10.0, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0020] The washing is alternating washing with hot water and cold water, and the washing is stopped until no AgCl precipitate is detected by 0.1M silver nitrate solution.

[0021] In some optional embodiments, the temperature of the hot water used in the washing is 60-70℃, which can be 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃ or 70℃, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0022] As a preferred technical solution of the present application, in step S2, the concentration of the Tris-HCl solution is 30-70mM, which can be 30mM, 34mM, 38mM, 42mM, 46mM, 50mM, 54mM, 58mM, 62mM, 66mM or 70mM, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0023] In some optional embodiments, the pH value of the Tris-HCl buffer solution is 8-9, which can be 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9 or 9.0, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0024] In some optional embodiments, the diameter of the wool fiber is 18.5-20.5μm, which can be 18.5μm, 18.7μm, 18.9μm, 19.1μm, 19.3μm, 19.5μm, 19.7μm, 19.9μm, 20.1μm, 20.3μm or 20.5μm, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0025] In some optional embodiments, the length of the wool fiber is 50-70mm, which can be 50mm, 52mm, 54mm, 56mm, 58mm, 60mm, 62mm, 64mm, 66mm, 68mm or 70mm, but is not limited to the listed values, and other values not listed in the range are also applicable. In some optional embodiments, the length of the wool fiber is 50-70mm, which can be 50mm, 52mm, 54mm, 56mm, 58mm, 60mm, 62mm, 64mm, 66mm, 68mm or 70mm, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0026] In some alternative embodiments, the mass-volume ratio of the wool fibers to the Tris-HCl buffer solution is 1 g: (30-50) mL, for example, it can be 1 g:30 mL, 1 g:32 mL, 1 g:34 mL, 1 g:36 mL, 1 g:38 mL, 1 g:40 mL, 1 g:42 mL, 1 g:44 mL, 1 g:46 mL, 1 g:48 mL or 1 g:50 mL, but not limited to the listed values, other values not listed in the range are also applicable.

[0027] In some alternative embodiments, the concentration of tea polyphenols in the reaction solution C is 1-4 g / L, for example, it can be 1.0 g / L, 1.3 g / L, 1.6 g / L, 1.9 g / L, 2.2 g / L, 2.5 g / L, 2.8 g / L, 3.1 g / L, 3.4 g / L, 3.7 g / L or 4.0 g / L, but not limited to the listed values, other values not listed in the range are also applicable.

[0028] In some alternative embodiments, the stirring speed of the reaction solution C is 50-100 rpm, for example, it can be 50 rpm, 55 rpm, 60 rpm, 65 rpm, 70 rpm, 75 rpm, 80 rpm, 85 rpm, 90 rpm, 95 rpm or 100 rpm, but not limited to the listed values, other values not listed in the range are also applicable.

[0029] In some alternative embodiments, the stirring time of the reaction solution C is 8-12 h, for example, it can be 8.0 h, 8.4 h, 8.8 h, 9.2 h, 9.6 h, 10.0 h, 10.4 h, 10.8 h, 11.2 h, 11.6 h or 12.0 h, but not limited to the listed values, other values not listed in the range are also applicable.

[0030] As a preferred technical solution of the present application, in step S3, the stirring time of the sodium alginate in the deionized water is 2-4 h, for example, it can be 2.0 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3.0 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h or 4.0 h, but not limited to the listed values, other values not listed in the range are also applicable.

[0031] In some optional embodiments, the time for stirring the sodium alginate in the deionized water is 16-20 h, for example, can be 16.0 h, 16.4 h, 16.8 h, 17.2 h, 17.6 h, 18.0 h, 18.4 h, 18.8 h, 19.2 h, 19.6 h or 20.0 h, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0032] In some optional embodiments, the mass fraction of the sodium alginate solution is 4-8 wt.%, for example, can be 4.0 wt.%, 4.4 wt.%, 4.8 wt.%, 5.2 wt.%, 5.6 wt.%, 6.0 wt.%, 6.4 wt.%, 6.8 wt.%, 7.2 wt.%, 7.6 wt.% or 8.0 wt.%, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0033] In some optional embodiments, the concentration of the aqueous acetic acid solution is 1-2%, for example, can be 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2.0%, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0034] In some optional embodiments, the time for stirring the chitosan in the aqueous acetic acid solution is 3-6 h, for example, can be 3.0 h, 3.3 h, 3.6 h, 3.9 h, 4.2 h, 4.5 h, 4.8 h, 5.1 h, 5.4 h, 5.7 h or 6.0 h, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0035] In some optional embodiments, the mass fraction of the chitosan solution is 2-4 wt.%, for example, can be 2.0 wt.%, 2.2 wt.%, 2.4 wt.%, 2.6 wt.%, 2.8 wt.%, 3.0 wt.%, 3.2 wt.%, 3.4 wt.%, 3.6 wt.%, 3.8 wt.% or 4.0 wt.%, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0036] In some optional embodiments, the mass ratio of sodium alginate to chitosan in the mixed spinning dope is (80-90):(20-10), for example, can be 80:20, 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11 or 90:10, but not limited to the listed values, other values not listed in the range of values are also applicable.

[0037] In some alternative embodiments, the bolus speed of the syringe pump is 0.1-0.5 mL / min, for example, it can be 0.10 mL / min, 0.14 mL / min, 0.18 mL / min, 0.22 mL / min, 0.26 mL / min, 0.30 mL / min, 0.34 mL / min, 0.38 mL / min, 0.42 mL / min, 0.46 mL / min, or 0.50 mL / min, but is not limited to the listed values, other values not listed in the range are also applicable.

[0038] In some alternative embodiments, the orifice diameter of the syringe pump is 80-150 μm, for example, it can be 80 μm, 87 μm, 94 μm, 101 μm, 108 μm, 115 μm, 122 μm, 129 μm, 136 μm, 143 μm, or 150 μm, but is not limited to the listed values, other values not listed in the range are also applicable.

[0039] In some alternative embodiments, the coagulation liquid is an aqueous ethanol solution of calcium chloride, and the mass fraction of the coagulation liquid is 2-5 wt.%, for example, it can be 2.0 wt.%, 2.3 wt.%, 2.6 wt.%, 2.9 wt.%, 3.2 wt.%, 3.5 wt.%, 3.8 wt.%, 4.1 wt.%, 4.4 wt.%, 4.7 wt.%, or 5.0 wt.%, but is not limited to the listed values, other values not listed in the range are also applicable.

[0040] In some alternative embodiments, the volume ratio of ethanol to water in the coagulation liquid is (30-50):(70-50), for example, it can be 30:70, 32:68, 34:66, 36:64, 38:62, 40:60, 42:58, 44:56, 46:54, 48:52, or 50:50, but is not limited to the listed values, other values not listed in the range are also applicable.

[0041] In some alternative embodiments, the nascent fiber is subjected to the second drawing in water at 60-80 °C, for example, it can be subjected to the second drawing in water at 60 °C, 62 °C, 64 °C, 66 °C, 68 °C, 70 °C, 72 °C, 74 °C, 76 °C, 78 °C, or 80 °C, but is not limited to the listed values, other values not listed in the range are also applicable.

[0042] In some optional embodiments, the draw ratio of the first drawing is 1.1-1.5 times, for example, it can be 1.10 times, 1.14 times, 1.18 times, 1.22 times, 1.26 times, 1.30 times, 1.34 times, 1.38 times, 1.42 times, 1.46 times or 1.50 times, but not limited to the listed values, and other values not listed in the range are also applicable.

[0043] In some optional embodiments, the draw ratio of the second drawing is 2-4 times, for example, it can be 2.0 times, 2.2 times, 2.4 times, 2.6 times, 2.8 times, 3.0 times, 3.2 times, 3.4 times, 3.6 times, 3.8 times or 4.0 times, but not limited to the listed values, and other values not listed in the range are also applicable.

[0044] As a preferred technical solution of the present application, in step S4, the mass ratio of the modified hemp fibers to the modified wool fibers is (4-6):(6-4), for example, it can be 4:6, 4.2:5.8, 4.4:5.6, 4.6:5.4, 4.8:5.2, 5:5, 5.2:4.8, 5.4:4.6, 5.6:4.4, 5.8:4.2 or 6:4, but not limited to the listed values, and other values not listed in the range are also applicable.

[0045] The alginate / chitosan composite filament is a core yarn;

[0046] In some optional embodiments, the weight percentage of the alginate / chitosan composite filament in the odor-resistant bio-based wool blended yarn is 8-15%, for example, it can be 8.0%, 8.7%, 9.4%, 10.1%, 10.8%, 11.5%, 12.2%, 12.9%, 13.6%, 14.3% or 15.0%, but not limited to the listed values, and other values not listed in the range are also applicable.

[0047] In a second aspect, the present application provides an odor-resistant bio-based wool blended yarn.

[0048] The present application selects hemp fibers, wool fibers and alginate / chitosan composite filaments as the main materials. The odor-resistant bio-based wool blended yarn is obtained by taking the alginate / chitosan composite filament as the core yarn and coating the hemp fibers and the wool fibers.

[0049] Hemp fibers have excellent antibacterial properties, air permeability and sustainability, but also have deficiencies that need to be modified in practical applications: first, hemp fiber bundles contain a large amount of pectin and lignin, and the structure of cellulose I (natural crystal form) is regular, resulting in strong rigidity and poor skin affinity; second, hemp fibers are stiff and have insufficient cohesion, which can easily produce hair and broken ends during spinning. Traditional modification methods (such as strong alkali treatment, biological enzyme degumming) more or less have problems of environmental pollution, damage to the main body of the fiber, or incomplete effect.

[0050] In this application, ionic liquid is used to change the surface physical structure of hemp fibers, converting them from "hard fibers" to "flexible fibers", achieving permanent and structural softening, and greatly improving their moisture absorption and moisture release performance. Ionic liquid [Bmim]Cl is an organic salt, and its chloride ion as a strong hydrogen bond acceptor can effectively destroy the hydrogen bond network between and within the molecular chains of hemp cellulose. The cation [Bmim] + The volume is large, and it can insert between the opened molecular chains to prevent them from re-aggregating. Under heating conditions of 90-110℃, this process is accelerated, and by controlling the treatment time, "surface solution plasticization" is achieved: only the cellulose on the surface and subsurface of the fiber is dissolved, while the skeleton structure of the fiber core remains intact.

[0051] When the treatment system is poured into a large amount of water, water as a strong polar protic solvent has a much greater affinity for ionic liquid than for cellulose. Water molecules will quickly combine with the ionic liquid that has combined with the cellulose, causing the dissolved cellulose molecular chains to lose support and precipitate on the fiber surface. Because the precipitation process is rapid and disordered, the cellulose molecular chains will arrange in a thermodynamically more stable but more loosely structured cellulose II crystal form. The natural cellulose I crystal form is arranged in parallel, with a tight structure, so it is stiff. The regenerated cellulose II crystal form is arranged in an anti-parallel manner, with weaker intermolecular forces, so it is soft and elastic. This application is equivalent to constructing a naturally soft cellulose II structure layer on the hard hemp fiber in situ, which is made of its own material. This softness comes from a fundamental change in crystal form, so it is permanent and extremely wash-resistant. At the same time, the regenerated surface forms a nano-porous structure, greatly improving the specific surface area and capillary effect.

[0052] Wool has natural antibacterial properties, but under extreme conditions such as excessive sweating, it can still produce odors. Traditional odor-resistant finishing relies on silver ions, quaternary ammonium salts, etc., which have biological accumulation risks and wash resistance decay problems. In this application, natural and edible tea polyphenols are used to "grow" a layer of multifunctional nano-biological film on the surface of wool fibers in situ, achieving long-lasting antioxidant and odor-resistant, natural UV protection, and gentle modification of the wool scale layer in one step.

[0053] Tea polyphenols are rich in phenolic hydroxyl groups, which can be deprotonated to form phenolic oxygen anions under weak alkaline and aerobic conditions. These anions are easily oxidized to semiquinone free radicals and further oxidized to highly active quinone structures. These highly active quinone structures can undergo free radical polymerization or nucleophilic addition reactions and are connected to each other to form a polyphenol network, i.e., a nanometer-thin film. More importantly, quinone structures are strong Michael acceptors, and the keratin of wool is rich in nucleophilic amino and sulfhydryl groups. These groups can undergo Michael addition reactions or Schiff base reactions with quinone structures to form stable covalent bonds. This enables the polyphenol film to be attached to the surface of wool rather than simply physically adsorbed, thereby achieving extremely strong wash fastness.

[0054] In the present application, alginate / chitosan composite filaments are prepared by wet spinning as the core of yarn. Chitosan, as the core antibacterial agent, is firmly physically embedded and ionically cross-linked in the network framework composed of alginate, realizing non-dissolution, long-acting and strong antibacterial function.

[0055] Sodium alginate is a negatively charged polyanion in water, while chitosan is a positively charged polycation in acidic solution. When mixed, they form polyelectrolyte complexes through electrostatic attraction, laying the foundation for the uniformity and stability of the spinning solution; when the mixed spinning solution is extruded into a coagulation liquid containing divalent calcium ions, one calcium ion can simultaneously ionically bond with the carboxyl groups on two different alginate molecular chains, and numerous such "ionic bridges" rapidly cross-link the flowing molecular chains into a three-dimensional network structure, causing the liquid stream to solidify into a solid fiber. In this rapidly formed cross-linked network, chitosan molecules are physically embedded and entangled, and their own positive charges are also attracted to the negative charges of alginate, further stabilizing their position in the network. Subsequent hot water drawing takes advantage of the increased activity of polymer chains at high temperatures, and through the application of external force, disordered molecular chains are oriented along the fiber axis, increasing the van der Waals force between molecules, thereby greatly increasing the breaking strength and modulus of the fiber.

[0056] Finally, the modified hemp fibers, modified wool fibers, and alginate / chitosan composite filaments form a three-dimensional deodorization system through core spinning technology. In the modified wool fibers of the outer shell, the tea polyphenol coating serves as the first line of defense, preventing the decomposition of organic matter in sweat through antioxidant action and inhibiting the production of odor molecules from the source; the modified hemp fibers work synergistically with the modified wool fibers to create a dry and slightly acidic environment that is not conducive to the growth of bacteria; and the alginate / chitosan composite filaments, as the final line of defense, have their components serving their respective functions: chitosan can exert its strong and active contact sterilization effect to eliminate stubborn bacteria that penetrate the outer shell layer; and alginate can absorb and lock a large amount of water, keeping the skin surface and inner layer of the fabric dry and comfortable for a long time.

[0057] Compared with the prior art, the present application has the following advantages:

[0058] In order to solve the problem of rough touch and poor spinnability of natural hemp fibers caused by the rigid cellulose I crystal structure, the application uses ion liquid surface modification technology to selectively dissolve the surface layer of hemp fibers by using ion liquid, and then rapidly regenerates in water to promote the rearrangement of cellulose molecular chains and form cellulose II crystal structure with looser and softer structure. This "surface plasticizing" method of changing crystal structure not only permanently endows hemp fibers with extremely washable softness structure, but also constructs a nano-porous surface, thereby improving the skin comfort and moisture absorption and moisture release performance;

[0059] In order to overcome the environmental risk and functional attenuation problems of traditional deodorant finishing agents, the application utilizes the self-polymerization characteristics of natural tea polyphenol under weak alkaline aerobic conditions. After being oxidized into highly active quinone structure, it not only can crosslink to form a nano-film, but also can covalently bond with the amino and sulfhydryl groups in the wool keratin. This polyphenol coating which "grows in situ" and firmly connects to the fiber surface realizes the functions of long-lasting, wash-resistant antioxidant and deodorant, and natural UV protection in one step;

[0060] The application prepares alginate / chitosan composite filaments through wet spinning technology to construct a yarn core with long-lasting and non-dissolving antibacterial function. The uniform spinning solution is formed by the electrostatic attraction between negatively charged sodium alginate and positively charged chitosan. Then, in the coagulation bath containing calcium ions, the liquid flow is instantly coagulated into fibers through the rapid ionic crosslinking of calcium ions and alginate molecular chains. In this process, chitosan is physically embedded and locked in the network, ensuring the non-dissolution of its antibacterial function. Subsequent hot water drawing promotes the axial arrangement of high molecular chains, significantly improving the mechanical strength and modulus of the filaments;

[0061] The application obtains a synergistic three-dimensional deodorant system through core spinning technology. First, the modified wool in the outer shell uses its tea polyphenol coating as the first line of defense to inhibit odor generation from the source through antioxidant action. Second, the entire outer shell layer is created by modified hemp and wool to create a dry and antibacterial microenvironment. The core filament, as the final line of defense, can actively contact and kill bacteria that penetrate the defense line, while the alginate component can efficiently absorb and lock in moisture, ensuring long-lasting dryness and comfort. DETAILED DESCRIPTION

[0062] The technical solutions of the present application will be described in detail below with specific examples. The examples described herein are specific embodiments of the present application, which are used to illustrate the concept of the present application; these descriptions are all explanatory and exemplary, and should not be understood as limiting the embodiments of the present application and the protection scope of the present application. In addition to the examples described herein, those skilled in the art can also employ other technical solutions that are obvious based on the content disclosed in the claims and the description of the present application, which include technical solutions that make any obvious substitutions and modifications to the examples described herein.

[0063] The chemical reagents used in the examples and comparative examples of the present application are all commercially available products without further purification or treatment.

[0064] Example 1

[0065] The present example provides a deodorant bio-based wool blended yarn and a preparation method thereof, and the preparation method of the deodorant bio-based wool blended yarn specifically comprises the following steps:

[0066] S1: hemp fibers with a length of 40 mm and a fineness of 10 dtex are soaked in deionized water at 75℃ for 0.8h, and dried to obtain pretreated hemp fibers; the pretreated hemp fibers are added to ionic liquid [Bmim]Cl and stirred at 105℃ and a rotation speed of 150 rpm for 6 min to obtain reaction liquid A, wherein the mass ratio of the pretreated hemp fibers to the ionic liquid is 1:30, the reaction liquid A is mixed with deionized water at a volume ratio of 1:8 and stirred, and then filtered, washed and dried to obtain modified hemp fibers, wherein the washing is alternating washing with hot water at 65℃ and cold water;

[0067] S2: a Tris-HCl solution with a concentration of 50mM is prepared, and the pH value is adjusted to 8.5 to obtain a Tris-HCl buffer solution; wool fibers with a diameter of 19.0μm and a length of 60mm are soaked in the Tris-HCl buffer solution to obtain reaction liquid B, wherein the mass-volume ratio of the wool fibers to the Tris-HCl buffer solution is 1g:40mL, tea polyphenols are added to obtain reaction liquid C, wherein the concentration of the tea polyphenols in the reaction liquid C is 3.5g / L, and the reaction is stirred at a rotation speed of 80 rpm for 10h, and then filtered, washed and dried to obtain modified wool fibers;

[0068] S3: Sodium alginate was put into deionized water, stirred for 3 h and then placed for 18 h to obtain a sodium alginate solution with a mass fraction of 6 wt.%; chitosan was put into an acetic acid aqueous solution with a concentration of 1.5%, stirred for 5 h and then placed to obtain a chitosan solution with a mass fraction of 3 wt.%; the chitosan solution was added to the sodium alginate solution to mix uniformly, and vacuum defoaming was performed to obtain a mixed spinning dope, wherein the mass ratio of sodium alginate to chitosan in the mixed spinning dope was 85:15, the mixed spinning dope was loaded into a syringe pump, and a constant speed of 0.3 mL / min was used for injection to obtain a stream that passed through a coagulation liquid to obtain a nascent fiber, wherein the nozzle diameter of the syringe pump was 100 μm, the coagulation liquid was a calcium chloride ethanol aqueous solution with a mass fraction of 3 wt.%, and the volume ratio of ethanol to water was 40:60; the nascent fiber was subjected to a first drawing in the coagulation liquid and then subjected to a second drawing in water at 70℃ to obtain a pretreated composite filament, wherein the drawing ratio of the first drawing was 1.3 times, and the drawing ratio of the second drawing was 3 times, and then washing, oiling and drying were performed to obtain a sodium alginate / chitosan composite filament;

[0069] S4: The modified hemp fibers and the modified wool fibers were mixed in a mass ratio of 5:5, opened, carded and drawn to obtain a fiber strip, and the fiber strip and the sodium alginate / chitosan composite filament were spun using a ring spinning device to obtain an odor-resistant bio-based wool blended yarn; wherein the sodium alginate / chitosan composite filament was a core yarn, and the weight percentage in the yarn was 10%.

[0070] Example 2

[0071] The embodiment provides an odor-resistant bio-based wool blended yarn and a preparation method thereof, and the preparation method of the odor-resistant bio-based wool blended yarn specifically comprises the following steps:

[0072] S1: Hemp fibers with a length of 50 mm and a fineness of 5 dtex were soaked in deionized water at 60℃ for 1 h, and then dried to obtain pretreated hemp fibers; the pretreated hemp fibers were added to an ionic liquid [Bmim]Cl, stirred at 90℃ and a rotation speed of 200 rpm for 3 min to obtain a reaction liquid A, wherein the mass ratio of the pretreated hemp fibers to the ionic liquid was 1:50, the reaction liquid A was mixed with deionized water in a volume ratio of 1:5 and stirred, and then filtered, washed and dried to obtain modified hemp fibers, wherein the washing was performed by alternating hot water at 70℃ and cold water;

[0073] S2: a Tris-HCl solution with a concentration of 70 mM was prepared and the pH value was adjusted to 9 to obtain a Tris-HCl buffer solution; wool fibers with a diameter of 20.5 μm and a length of 50 mm were immersed in the Tris-HCl buffer solution to obtain a reaction liquid B, wherein the mass-volume ratio of the wool fibers to the Tris-HCl buffer solution was 1 g:30 mL, tea polyphenols were added to obtain a reaction liquid C, wherein the concentration of the tea polyphenols in the reaction liquid C was 1 g / L, and the reaction was stirred at a rotating speed of 50 rpm for 12 h, followed by filtration, washing, and drying to obtain modified wool fibers;

[0074] S3: sodium alginate was put into deionized water, stirred for 4 h, and then statically placed for 16 h to obtain a sodium alginate solution with a mass fraction of 8 wt.%; chitosan was put into an acetic acid aqueous solution with a concentration of 2%, stirred for 3 h, and then statically placed to obtain a chitosan solution with a mass fraction of 4 wt.%; the chitosan solution was added to the sodium alginate solution and uniformly mixed, and vacuum defoaming was performed to obtain a mixed spinning dope, wherein the mass ratio of sodium alginate to chitosan in the mixed spinning dope was 90:10; the mixed spinning dope was loaded into a syringe pump, and a fine stream obtained by constant-speed injection at a rate of 0.5 mL / min was subjected to coagulation to obtain a nascent fiber, wherein the nozzle diameter of the syringe pump was 150 μm, and the coagulation liquid was a calcium chloride ethanol aqueous solution with a mass fraction of 5 wt.%, and the volume ratio of ethanol to water was 50:50; the nascent fiber was subjected to a first drawing in the coagulation liquid and then subjected to a second drawing in water at 60℃ to obtain a pretreated composite filament, wherein the drawing ratio of the first drawing was 1.5 times, and the drawing ratio of the second drawing was 2 times, followed by washing, oiling, and drying to obtain an alginate / chitosan composite filament;

[0075] S4: the modified hemp fibers and the modified wool fibers were mixed at a mass ratio of 6:4, opened, carded, and drawn to obtain a fiber strip, and the alginate / chitosan composite filament was spun into an odor-resistant bio-based wool blended yarn using a ring spinning device; wherein the alginate / chitosan composite filament was a core yarn, and the weight percentage in the yarn was 15%.

[0076] Example 3

[0077] The embodiment provides an odor-resistant bio-based wool blended yarn and a preparation method thereof.

[0078] S1: hemp fibers with length of 35 mm and fineness of 8 dtex were soaked in deionized water at 65℃ for 0.6 h, and dried to obtain pretreated hemp fibers; the pretreated hemp fibers were added into ionic liquid [Bmim]Cl to obtain reaction liquid A at 95℃ and stirring speed of 120 rpm for 5 min, wherein the mass ratio of the pretreated hemp fibers to the ionic liquid was 1:40, the reaction liquid A was mixed with deionized water at a volume ratio of 1:7 and stirred, and then the modified hemp fibers were obtained by filtration, washing and drying, wherein the washing was performed by alternating washing with hot water at 62℃ and cold water;

[0079] S2: a Tris-HCl solution with a concentration of 40 mM was prepared, and the pH value was adjusted to 8.2 to obtain a Tris-HCl buffer solution; wool fibers with a diameter of 19.5 μm and a length of 65 mm were soaked in the Tris-HCl buffer solution to obtain reaction liquid B, wherein the mass-volume ratio of the wool fibers to the Tris-HCl buffer solution was 1 g:35 mL, and tea polyphenols were added to obtain reaction liquid C, wherein the concentration of the tea polyphenols in the reaction liquid C was 2.5 g / L, and the reaction was stirred at a stirring speed of 90 rpm for 9 h, and then the modified wool fibers were obtained by filtration, washing and drying;

[0080] S3: sodium alginate was put into deionized water, stirred for 2.5 h, and then statically placed for 19 h to obtain a sodium alginate solution with a mass fraction of 5 wt.%; chitosan was put into an acetic acid aqueous solution with a concentration of 1.8%, stirred for 4 h, and then statically placed to obtain a chitosan solution with a mass fraction of 2.5 wt.%; the chitosan solution was added into the sodium alginate solution, uniformly mixed, and vacuum defoamed to obtain a mixed spinning dope, wherein the mass ratio of sodium alginate to chitosan in the mixed spinning dope was 82:18; the mixed spinning dope was loaded into a syringe pump, and a fine stream obtained by constant-speed injection at a rate of 0.2 mL / min was subjected to a coagulating liquid to obtain a nascent fiber, wherein the nozzle diameter of the syringe pump was 120 μm, and the coagulating liquid was a calcium chloride ethanol aqueous solution with a mass fraction of 4 wt.%, and the volume ratio of ethanol to water was 35:65; the nascent fiber was subjected to a first drawing in the coagulating liquid, and then subjected to a second drawing in water at 75℃ to obtain a pretreated composite filament, wherein the drawing ratio of the first drawing was 1.2 times, and the drawing ratio of the second drawing was 3.5 times, and then the pretreated composite filament was subjected to washing, oiling and drying to obtain a alginate / chitosan composite filament;

[0081] S4: the modified hemp fibers and the modified wool fibers were mixed at a mass ratio of 4.5:5.5, opened, carded and drawn to obtain a fiber strip, and the fiber strip and the alginate / chitosan composite filament were spun to obtain an odor-resistant bio-based wool blended yarn using a ring spinning device; wherein the alginate / chitosan composite filament was a core yarn, and the weight ratio of the alginate / chitosan composite filament in the yarn was 12%.

[0082] Example 4

[0083] The embodiment provides a deodorant bio-based wool blended yarn and a preparation method thereof, and the preparation method of the deodorant bio-based wool blended yarn specifically comprises the following steps.

[0084] S1: hemp fibers with a length of 30 mm and a fineness of 15 dtex are soaked in deionized water at 80 DEG C for 0.5 h, and dried to obtain pretreated hemp fibers; the pretreated hemp fibers are added into an ionic liquid [Bmim]Cl, stirred at 110 DEG C and a rotating speed of 100 rpm for 8 min to obtain a reaction liquid A, wherein the mass ratio of the pretreated hemp fibers to the ionic liquid is 1:20, the reaction liquid A is mixed with deionized water at a volume ratio of 1:10 and stirred, and then filtered, washed and dried to obtain modified hemp fibers, wherein the washing is carried out by alternately washing with hot water at 60 DEG C and cold water;

[0085] S2: a Tris-HCl solution with a concentration of 30 mM is prepared, and the pH value is adjusted to 8 to obtain a Tris-HCl buffer solution; wool fibers with a diameter of 18.5 mu m and a length of 70 mm are soaked in the Tris-HCl buffer solution to obtain a reaction liquid B, wherein the mass-volume ratio of the wool fibers to the Tris-HCl buffer solution is 1 g:50 mL, and tea polyphenol is added to obtain a reaction liquid C, wherein the concentration of the tea polyphenol in the reaction liquid C is 4 g / L, and the reaction is stirred at a rotating speed of 100 rpm for 8 h, and then filtered, washed and dried to obtain modified wool fibers;

[0086] S3: sodium alginate is put into deionized water, stirred for 2 h, and then placed for 20 h to obtain a sodium alginate solution with a mass fraction of 4 wt.%; chitosan is put into an acetic acid aqueous solution with a concentration of 1%, stirred for 6 h, and then placed to obtain a chitosan solution with a mass fraction of 2 wt.%; the chitosan solution is added into the sodium alginate solution, uniformly mixed, and vacuum degassed to obtain a mixed spinning stock solution, wherein the mass ratio of sodium alginate to chitosan in the mixed spinning stock solution is 80:20; the mixed spinning stock solution is loaded into a syringe pump, and a jet flow obtained by constant-speed injection at a rate of 0.1 mL / min is subjected to coagulation liquid to obtain a nascent fiber, wherein the nozzle diameter of the syringe pump is 80 mu m, the coagulation liquid is a calcium chloride ethanol aqueous solution with a mass fraction of 2 wt.%, and the volume ratio of ethanol to water is 30:70; the nascent fiber is subjected to first drawing in the coagulation liquid, and then subjected to second drawing in water at 80 DEG C to obtain a pretreated composite filament, wherein the drawing ratio of the first drawing is 1.1 times, and the drawing ratio of the second drawing is 4 times; and then, after washing, oiling and drying, a sodium alginate / chitosan composite filament is obtained;

[0087] S4: the modified hemp fibers and the modified wool fibers are mixed at a mass ratio of 4:6, opened, carded and drawn to obtain a fiber strip, and the fiber strip and the sodium alginate / chitosan composite filament are spun by using a ring spinning device to obtain a deodorant bio-based wool blended yarn; wherein the sodium alginate / chitosan composite filament is a core yarn, and the weight proportion of the sodium alginate / chitosan composite filament in the yarn is 8%.

[0088] Comparative Example 1

[0089] The present comparative example provides a deodorant bio-based wool blended yarn and a preparation method thereof, which is different from Example 1 in that in S1, a sodium hydroxide solution with a concentration of 10-20% is used to replace the ionic liquid [Bmim]Cl to treat the hemp fibers, and other operation steps and process parameters are exactly the same as those of Example 1.

[0090] Comparative Example 2

[0091] The present comparative example provides a deodorant bio-based wool blended yarn and a preparation method thereof, which is different from Example 1 in that in S4, unmodified hemp fibers are directly used, and other operation steps and process parameters are exactly the same as those of Example 1.

[0092] Comparative Example 3

[0093] The present comparative example provides a deodorant bio-based wool blended yarn and a preparation method thereof, which is different from Example 1 in that in S2, a nano-silver antibacterial finishing agent is used to modify the surface of the wool fibers, and other operation steps and process parameters are exactly the same as those of Example 1.

[0094] Comparative Example 4

[0095] The present comparative example provides a deodorant bio-based wool blended yarn and a preparation method thereof, which is different from Example 1 in that in S4, unmodified wool fibers are directly used, and other operation steps and process parameters are exactly the same as those of Example 1.

[0096] The deodorant bio-based wool blended yarns of Examples 1-4 and Comparative Examples 1-4 are tested for performance, and the specific process is as follows:

[0097] The single yarn breaking strength and single yarn breaking strength variation coefficient of the sample are tested according to GB / T 3916-2013;

[0098] The strip evenness variation coefficient of the sample is tested according to GB / T 3292.1-2008;

[0099] The deodorant antibacterial performance of the sample is tested according to GB / T 20944.3-2008.

[0100] The test results are shown in Table 1.

[0101] Table 1 Performance test results of deodorant bio-based wool blended yarns of Examples 1-4 and Comparative Examples 1-4

[0102]

[0103] From the test results of Example 1 and Comparative Example 1, it can be seen that when sodium hydroxide solution is selected instead of ionic liquid to modify hemp fibers, this severe chemical etching process not only removes pectin and lignin, but also seriously degrades cellulose, resulting in damage to the natural high strength of hemp fibers. The damaged fibers are more prone to breakage during spinning, forming weak loops, thus reducing the overall strength of the final yarn; although strong alkali treatment can remove part of the gum, its effect is not uniform and controllable. Part of the fiber bundle may be over-treated and become brittle, and part may be under-treated and remain stiff. This non-uniformity causes the fibers to behave extremely unstable during drafting, forming a large number of thick and thin sections, thus the breaking strength variation coefficient and the evenness variation coefficient of the yarn increase; the final antibacterial performance of the yarn is mainly determined by the tea polyphenol modified wool and the core silk. The modification method of hemp fibers mainly affects the physical properties and comfort, and has little effect on the antibacterial performance of the final yarn.

[0104] From the test results of Example 1 and Comparative Example 2, it can be seen that directly using unmodified hemp fibers, although the single fiber strength is high, but in the yarn, its stiff and poor cohesion characteristics cause the load to be unable to be effectively transmitted between fibers. The yarn is more prone to breakage due to fiber slippage, and its breaking strength decreases; the unmodified raw hemp fiber bundle is extremely difficult to be effectively separated and controlled during carding and drafting, interfering with the normal movement of the fibers, resulting in serious unevenness of the yarn, and further causing the yarn strength to be extremely unstable, i.e. the breaking strength variation coefficient and the evenness variation coefficient of the yarn increase; the effect on the antibacterial performance is small.

[0105] From the test results of Example 1 and Comparative Example 3, it can be seen that nano-silver finishing is a surface deposition technology, which has little effect on the physical properties of wool fibers; freshly prepared nano-silver particles have extremely high specific surface area and biological activity, and their initial bactericidal efficiency is very high; however, the combination of nano-silver particles and wool fibers is mainly physical adsorption and van der Waals force, and the binding force is weak. Under the action of repeated mechanical rubbing and chemical detergents, nano-silver particles will gradually fall off and lose, resulting in a decrease in antibacterial performance with an increase in washing times.

[0106] From the test results of Example 1 and Comparative Example 4, it can be seen that tea polyphenol modification is a nanoscale surface treatment, which has little effect on the physical properties of wool. Therefore, using raw wool, the physical properties of the yarn change little; lacking the broad-spectrum bacteriostatic and antioxidant (odor suppression from the source) effects of tea polyphenol, the initial antibacterial performance is weakened, and the persistent bacteriostatic effect almost completely depends on the core silk; lacking the protection of tea polyphenol, the antibacterial rate decreases after 100 washes.

[0107] The above merely describes the specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and it should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily conceived by those skilled in the art, and all such changes and replacements fall within the protection scope and disclosure scope of the present application.

Claims

1. A process for the preparation of an odor-resistant bio-based wool blend yarn characterized in that, The preparation method comprises: S1: hemp fibers are soaked in deionized water, dried to obtain pretreated hemp fibers; the pretreated hemp fibers are added into ionic liquid [Bmim]Cl to obtain reaction liquid A, the reaction liquid A is mixed with deionized water and stirred, filtered, washed with hot water and cold water alternately at 60-70 DEG C, and dried to obtain modified hemp fibers; S2: a Tris-HCl solution is prepared, and the pH value is adjusted to obtain a Tris-HCl buffer solution; wool fibers are soaked in the Tris-HCl buffer solution to obtain reaction liquid B, tea polyphenol is added to obtain reaction liquid C, and after stirring and reaction, the reaction liquid C is filtered, washed, and dried to obtain modified wool fibers; S3: sodium alginate is put into deionized water, stirred, and then placed to obtain a sodium alginate solution; chitosan is put into an acetic acid aqueous solution, stirred, and then placed to obtain a chitosan solution; the chitosan solution is added into the sodium alginate solution, mixed uniformly, and vacuum degassed to obtain a mixed spinning dope, the mixed spinning dope is loaded into a syringe pump, and a stream obtained by pushing the syringe pump is subjected to primary drawing in a coagulating liquid and secondary drawing in water to obtain a pretreated composite filament, and then the pretreated composite filament is washed with water, oiled, and dried to obtain a sodium alginate / chitosan composite filament; S4: the modified hemp fibers and the modified wool fibers are mixed, opened, carded, and drawn to obtain a fiber strip, and the fiber strip and the sodium alginate / chitosan composite filament are spun by using a ring spinning device to obtain an odor-resistant bio-based wool blended yarn, wherein the sodium alginate / chitosan composite filament is used as a core yarn, and the hemp fibers and the wool fibers are wrapped to obtain the odor-resistant bio-based wool blended yarn; chitosan is physically embedded and ionically crosslinked in a network framework formed by sodium alginate, thereby achieving a non-dissolution, long-acting and strong antibacterial function.

2. A process for the preparation of an odor resistant bio-based wool blended yarn as claimed in claim 1, wherein, In S1, the mass ratio of the pretreated hemp fibers to the ionic liquid is 1:(20-50).

3. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S1, The temperature for stirring the pretreated hemp fibers in the ionic liquid [Bmim]Cl is 90-110 DEG C; The stirring speed for stirring the pretreated hemp fibers in the ionic liquid [Bmim]Cl is 100-200 rpm; The stirring time for stirring the pretreated hemp fibers in the ionic liquid [Bmim]Cl is 3-8 min.

4. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S1, the washing is washing with hot water and cold water alternately.

5. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S2, the mass-to-volume ratio of the wool fibers to the Tris-HCl buffer solution is 1 g:(30-50) mL.

6. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S2, the concentration of the tea polyphenol in the reaction liquid C is 1-4 g / L.

7. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S3, The mass ratio of sodium alginate to chitosan in the mixed spinning dope is (80-90):(20-10).

8. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S3, The coagulating liquid is an ethanol aqueous solution of calcium chloride, and the mass fraction of the coagulating liquid is 2-5 wt.%; The volume ratio of ethanol to water in the coagulating liquid is (30-50):(70-50).

9. A method of preparing an odor-resistant bio-based wool blend yarn according to claim 1, characterized in that, In S4, The mass ratio of the modified hemp fibers to the modified wool fibers is (4-6):(6-4); The sodium alginate / chitosan composite filament is used as the core yarn. The weight proportion of the alginate / chitosan composite filament in the deodorant bio-based wool blended yarn is 8-15%.

10. A deodorant bio-based wool blended yarn prepared by the preparation method according to any one of claims 1-9.

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