Multifunctional wool fabric and preparation method thereof

Abstract

The invention relates to a multifunctional wool fabric and a preparation method thereof, and belongs to the technical field of functional textiles. The preparation method comprises the following steps: S1, dropwise adding ethanolamine into a zinc nitrate solution for reaction to obtain zinc oxide sol; s2, adding baicalin into the zinc oxide sol for reaction to obtain composite sol; s3, adding graphene oxide into the composite sol for reaction to obtain modified graphene oxide dispersion liquid; s4, the wool fabric is soaked in the modified graphene oxide dispersion liquid for finishing, and the multifunctional wool fabric is obtained. The far infrared emissivity of the multifunctional wool fabric is 0.89-0.92, the bacteriostasis rate on escherichia coli is 99.9%, the surface resistance is 3 * 10 < 8 >-8 * 10 < 8 > omega, the ultraviolet protection factor is 60-75, and the multifunctional wool fabric has excellent far infrared, antibacterial, antistatic and anti-ultraviolet properties; after 50 times of washing, the far infrared emissivity is higher than 0.83, and the fabric has excellent washing resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of functional textiles, and in particular relates to a multifunctional wool fabric and a preparation method thereof. Background Art

[0002] As a natural protein fiber, wool fiber has excellent skin affinity, warmth retention, moisture absorption and perspiration wicking properties, and is hypoallergenic. The development of multifunctional wool fabrics with far-infrared, antibacterial, antistatic, and anti-UV properties can not only increase product added value, expand high-end application areas, and promote the transformation of the textile industry chain towards high added value, but also achieve functional synergy optimization through technological integration and innovation (such as nanomaterials and green modification processes), breaking through the bottlenecks of traditional textile technology. The antibacterial and anti-UV properties can enhance health protection levels, meet the needs of special occupational groups, and enhance wearing comfort with the help of far-infrared and antistatic properties, thereby improving people's quality of life.

[0003] Invention patent CN111519426A discloses a finishing process for far-infrared and negative ion wool sweaters. Tourmaline nanopowder dispersion, nano-TiO2 dispersion, and nano-ZnO dispersion are mixed with NJ101 room-temperature adhesive. The nanopowder is adhered to the surface of the wool fabric by padding. However, the adhesive coating has an adverse effect on the feel and breathability of the wool fabric.

[0004] Invention patent CN108049161A discloses a special sleeping pad for women during confinement and a method for making the same. The side of the sleeping pad body close to the human body is coated with a layer of health-care material. The pad is made by mixing ground negative ion powder, mugwort extract, aloe extract, ceramic clay, titanium dioxide, nano-silver negative ion powder, bentonite, cobalt oxide, and rhodonite. The mixture is then sprayed with a layer of health-care material on the surface of a skin-friendly fabric layer to make the sleeping pad. However, the above components are difficult to combine with the skin-friendly fabric and there is a risk of easy detachment.

[0005] Invention patent CN110791953A discloses a production process for negative ion far-infrared anti-UV wool sweaters. Nano far-infrared ceramic radiators, nano negative ion tourmaline powder, and benzotriazole compounds are coated on the surface of the wool sweater fabric via an SPSP adhesive. The resulting wool sweater not only has excellent stimulated emission of negative ions, far infrared rays, and UV protection, but the adhesive coating has an adverse effect on the feel and breathability of the wool fabric.

[0006] Therefore, the development of wool fabrics with far-infrared, antibacterial, antistatic and anti-ultraviolet functions is of great significance, but there are great challenges. Summary of the Invention

[0007] To solve the above technical problems, the present invention provides a multifunctional wool fabric and a preparation method thereof. Graphene oxide is modified synergistically by using zinc oxide sol and baicalin, and the wool fabric is modified by using a functional finishing liquid containing modified graphene oxide to prepare a wool fabric with far-infrared, antibacterial, antistatic and anti-ultraviolet functions.

[0008] The first object of the present invention is to provide a method for preparing a multifunctional wool fabric, comprising the following steps:

[0009] S1, adding ethanolamine dropwise to the zinc nitrate solution to react and obtain zinc oxide sol;

[0010] S2, adding baicalin to the zinc oxide sol described in S1 to react to obtain a composite sol;

[0011] S3, adding graphene oxide to the composite sol described in S2 to react to obtain a modified graphene oxide dispersion;

[0012] S4. Immersing the wool fabric in the modified graphene oxide dispersion described in S3 for finishing to obtain the multifunctional wool fabric.

[0013] In one embodiment of the present invention, in S1, the concentration of the zinc nitrate solution is 1 mol / L-2 mol / L. Increasing the amount of zinc nitrate helps to form zinc oxide sol to coat graphene oxide, but too high a concentration causes particle agglomeration. The solvent of the zinc nitrate solution is ethanol and ethylene glycol.

[0014] Furthermore, the amount of ethanol used is 40%-60% of the total solvent volume.

[0015] In one embodiment of the present invention, in S1, the molar ratio of zinc nitrate to ethanolamine is 1:(1.5-2.5); the dropping rate of ethanolamine is 1 mL / min-1.5 mL / min; ethanolamine is a chelating agent that can form a complex with zinc ions and generate nano zinc oxide sol after hydrolysis.

[0016] In one embodiment of the present invention, in S1, the reaction temperature is 50°C-70°C, and the reaction time is 3h-5h.

[0017] In one embodiment of the present invention, in S2, the amount of baicalin is 1wt%-1.5wt% of the zinc oxide sol; the glucuronic acid group and 5,6-dihydroxyflavone structure in the baicalin molecule can coordinate with the zinc ions on the surface of zinc oxide to form a stable composite sol. Increasing the amount of baicalin helps to form a chelate with the zinc oxide sol and helps to improve the functionality of the composite sol, but too high an amount is wasteful.

[0018] In one embodiment of the present invention, in S2, the reaction temperature is 50°C-70°C, and the reaction time is 1.5h-3h; a long reaction time is conducive to the formation of the chelate, but too long a reaction time is wasteful.

[0019] In one embodiment of the present invention, in S3, the amount of graphene oxide is 0.5wt%-1.5wt% of the composite sol; an increase in the amount of graphene oxide helps to further improve functionality, but too high an amount of graphene oxide cannot be dispersed evenly.

[0020] In one embodiment of the present invention, in S3, the reaction pH is 6.5-7.5, the temperature is 50°C-70°C, and the reaction time is 2h-3h; under this pH condition, it is helpful to promote the combination of carboxyl groups on the surface of graphene oxide and hydroxyl groups of zinc oxide sol through hydrogen bonding.

[0021] In one embodiment of the present invention, in S4, the bath ratio of the immersion is 1:(20-40), the temperature is 90°C-98°C, and the time is 40min-70min; under these temperature conditions, it is helpful to open the scale layer on the surface of the wool fiber, so that the baicalin-doped composite sol-coated graphene oxide particles diffuse into the interior of the wool fiber.

[0022] The second object of the present invention is to provide a multifunctional wool fabric prepared by the method.

[0023] In one embodiment of the present invention, the multifunctional wool fabric has a far-infrared emissivity of 0.89-0.92, an antibacterial rate against Escherichia coli of 99.9%, and a surface resistance of 3×10 8 Ω-8×10 8 Ω, the ultraviolet protection factor (UPF) is 60-75, with excellent far-infrared, antibacterial, antistatic and anti-UV properties; after 50 washes, the far-infrared emissivity is still higher than 0.83, with excellent water-washing resistance.

[0024] The technical solution of the present invention has the following advantages over the prior art:

[0025] (1) The preparation method described in the present invention uses a composite sol doped with baicalin to coat graphene oxide, and ethanolamine is used as a chelating agent to form a stable complex with zinc ions, which is then slowly hydrolyzed to form zinc oxide nanoparticles. The amino and hydroxyl groups of ethanolamine inhibit the agglomeration of zinc oxide particles through steric hindrance and electrostatic repulsion, forming a uniform and transparent sol.

[0026] (2) The preparation method described in the present invention forms a coordination chelate by the glucuronic acid group and 5,6-dihydroxyflavone structure in the baicalin molecule with the zinc ions in the zinc oxide sol, and the carboxyl groups on the surface of the graphene oxide form a hydrogen bond network with the hydroxyl groups in the composite sol. At the same time, the negative charge of the graphene oxide and the positive charge of the composite sol are enhanced by electrostatic attraction. Therefore, the baicalin-doped composite sol can be uniformly loaded on the surface of the graphene oxide to form a stable modified graphene oxide dispersion.

[0027] (3) The preparation method described in the present invention treats the wool fabric by an immersion method under high temperature conditions. The high temperature treatment opens the scale layer of the wool fiber, allowing the modified graphene oxide to diffuse into the interior of the wool fiber. After the modification is completed, the scale layer of the wool fiber closes, thereby enclosing the modified graphene oxide particles inside the wool fiber. The surface of the modified graphene oxide particles is rich in zinc ions and polyphenol structures, which can chelate with the wool fiber, thereby improving the water-washing resistance of the multifunctional wool fabric.

[0028] (4) The hybrid carbon structure of the nanographene oxide in the multifunctional wool fabric of the present invention can emit far-infrared rays of 8μm-14μm, which can promote blood circulation, and the π-π conjugated structure of the nanographene oxide forms a conductive path, which improves the antistatic properties of the wool fabric. Zinc oxide has an excellent ultraviolet shielding effect, and ultraviolet protection and far-infrared therapy are achieved simultaneously; in addition, the nanozinc oxide sol can produce hydroxyl radicals and superoxide radicals under the excitation of visible light, which destroy bacterial DNA. Baicalin can enhance the responsiveness of zinc oxide to visible light, solving the defect that traditional zinc oxide must have antibacterial properties under ultraviolet light excitation (photocatalytic antibacterial); and baicalin, as a natural polyphenol, can destroy the bacterial membrane structure, forming a synergistic effect with the photocatalytic antibacterial effect of zinc oxide; at the same time, the nanographene oxide sheet has sharp edges and can mechanically destroy the bacterial cell wall. The triple antibacterial mechanism increases the antibacterial rate to 99.9% and avoids the drug resistance of a single mechanism. DETAILED DESCRIPTION

[0029] The present invention will be further described below with reference to specific embodiments so that those skilled in the art can better understand and implement the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. It should be understood that the specific embodiments are only used to illustrate the present invention, and the embodiments are not intended to limit the present invention.

[0030] In the present invention, unless otherwise defined, technical and scientific terms used herein have the same meanings as commonly understood by one skilled in the art to which the present invention belongs.

[0031] In the present invention, unless stated otherwise, the term "and / or" used in the present invention includes any and all combinations of one or more of the associated listed items.

[0032] In the present invention, unless otherwise stated, the experimental methods used in the examples of the present invention are conventional methods unless otherwise stated, and the materials, reagents, etc. used are all commercially available unless otherwise stated.

[0033] In the present invention, unless otherwise specified, the pH adjuster used in the examples of the present invention is dilute nitric acid or ammonia water.

[0034] Example 1

[0035] The multifunctional wool fabric and preparation method thereof of the present embodiment include the following steps:

[0036] S1. Ethanolamine was added dropwise to a 1.5 mol / L zinc nitrate solution at a rate of 1.3 mL / min, and the mixture was reacted at 60° C. for 4 h to obtain a zinc oxide sol; wherein the solvents of the zinc nitrate solution were ethanol and ethylene glycol, the amount of ethanol was 50% of the total solvent volume, and the molar ratio of zinc nitrate to ethanolamine was 1:2;

[0037] S2. gradually adding baicalin to the zinc oxide sol and continuing the reaction for 2.5 hours to obtain a composite sol; wherein the amount of baicalin is 1.3 wt% of the zinc oxide sol;

[0038] S3, adding graphene oxide to the composite sol, adjusting the pH to 7, and then reacting at 60° C. for 2.5 hours to obtain a modified graphene oxide dispersion; wherein the amount of graphene oxide is 1 wt% of the composite sol;

[0039] S4. Immerse the wool fabric in the modified graphene oxide dispersion at a bath ratio of 1:30 and finish at 94° C. for 55 minutes to obtain a multifunctional wool fabric.

[0040] Example 2

[0041] The multifunctional wool fabric and preparation method thereof of the present embodiment include the following steps:

[0042] S1. Ethanolamine was added dropwise to a 1 mol / L zinc nitrate solution at a rate of 1 mL / min, and the mixture was reacted at 50°C for 5 h to obtain a zinc oxide sol; wherein the solvents of the zinc nitrate solution were ethanol and ethylene glycol, the amount of ethanol was 40% of the total solvent volume, and the molar ratio of zinc nitrate to ethanolamine was 1:1.5;

[0043] S2. gradually adding baicalin to the zinc oxide sol and continuing the reaction for 3 hours to obtain a composite sol; wherein the amount of baicalin is 1 wt% of the zinc oxide sol;

[0044] S3, adding graphene oxide to the composite sol, adjusting the pH to 6.5, and then reacting at 50° C. for 3 h to obtain a modified graphene oxide dispersion; wherein the amount of graphene oxide is 0.5 wt% of the composite sol;

[0045] S4. Immerse the wool fabric in the modified graphene oxide dispersion at a bath ratio of 1:20 and finish at 90° C. for 70 minutes to obtain a multifunctional wool fabric.

[0046] Example 3

[0047] The multifunctional wool fabric and preparation method thereof of the present embodiment include the following steps:

[0048] S1. Ethanolamine was added dropwise to a 2 mol / L zinc nitrate solution at a rate of 1.5 mL / min, and the mixture was reacted at 70° C. for 3 h to obtain a zinc oxide sol; wherein the solvents of the zinc nitrate solution were ethanol and ethylene glycol, the amount of ethanol was 60% of the total solvent volume, and the molar ratio of zinc nitrate to ethanolamine was 1:2.5;

[0049] S2. gradually adding baicalin to the zinc oxide sol and continuing the reaction for 1.5 h to obtain a composite sol; wherein the amount of baicalin is 1.5 wt % of the zinc oxide sol;

[0050] S3, adding graphene oxide to the composite sol, adjusting the pH to 7.5, and then reacting at 70° C. for 2 h to obtain a modified graphene oxide dispersion; wherein the amount of graphene oxide is 1.5 wt % of the composite sol;

[0051] S4. Immerse the wool fabric in the modified graphene oxide dispersion at a bath ratio of 1:40 and finish at 98° C. for 40 minutes to obtain a multifunctional wool fabric.

[0052] Comparative Example 1

[0053] The process is basically the same as Example 1, except that zinc nitrate is replaced by sodium nitrate.

[0054] Comparative Example 2

[0055] The process is basically the same as Example 1, except that ethanolamine is replaced by ammonia water.

[0056] Comparative Example 3

[0057] The process is basically the same as Example 1, except that baicalin is not added.

[0058] Comparative Example 4

[0059] The method is basically the same as Example 1, except that graphene oxide is replaced by nano-titanium dioxide.

[0060] Comparative Example 5

[0061] The method is basically the same as Example 1, except that ethanolamine, baicalin and graphene oxide are simultaneously dissolved in zinc nitrate solution to obtain a finishing solution.

[0062] Comparative Example 6

[0063] The process is basically the same as in Example 1, except that the immersion temperature is adjusted to 60°C.

[0064] Comparative Example 7

[0065] The method is basically the same as Example 1, except that the graphene oxide is not modified.

[0066] Test Example 1

[0067] The flame retardant properties of the multifunctional wool fabrics (modified wool fabrics) and unmodified wool fabrics prepared in Examples 1-3 and Comparative Examples 1-7 were tested:

[0068] Far-infrared emissivity of fabrics: measured in accordance with GB / T 30127-2013 “Testing and evaluation of far-infrared properties of textiles”;

[0069] Antibacterial rate of fabric against Escherichia coli: measured according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method";

[0070] Surface resistance of fabric: Determined in accordance with GB / T 12703.1-2021 "Test method for electrostatic properties of textiles - Part 1: Static voltage half-life";

[0071] Ultraviolet protection factor (UPF) of fabrics: measured in accordance with GB / T 18830-2009 “Evaluation of UV protection properties of textiles”;

[0072] Washing method: Determined according to AATCC 61-2006 "Accelerated Test for Color Fastness to Washing for Household and Commercial Use".

[0073] Table 1 shows the relevant properties of the modified wool fabric and the unmodified wool fabric finally measured, where 0 times and 50 times are the number of washes:

[0074] Table 1

[0075]

[0076]

[0077] As can be seen from Table 1, the far infrared emissivity of the multifunctional wool fabric of the embodiment is 0.89-0.92, the antibacterial rate against Escherichia coli is 99.9%, and the surface resistance is 3×10 8 Ω-8×10 8 Ω, the ultraviolet protection factor (UPF) is 60-75, with excellent far-infrared, antibacterial, antistatic and anti-UV properties; after 50 washes, the far-infrared emissivity is still higher than 0.83, with excellent water-washing resistance.

[0078] Comparing Example 1 with Comparative Example 1, it can be seen that replacing zinc nitrate with sodium nitrate reduces the functionality and washability of the modified wool fabric. This is because sodium nitrate cannot form a stable sol and cannot effectively modify graphene oxide, causing the graphene oxide to easily agglomerate, making it difficult to apply to wool fabrics.

[0079] Comparing Example 1 and Comparative Example 2, it can be seen that when ethanolamine is replaced with ammonia, the functionality and washability of the modified wool fabric are reduced. This is because ammonia has difficulty chelating with zinc ions, resulting in poor stability of the zinc oxide particles, making it difficult to effectively coat the graphene oxide.

[0080] Comparison of Example 1 and Comparative Example 3 shows that without the addition of baicalin, the functionality of the modified wool fabric is reduced, especially its antibacterial properties. This is because zinc oxide requires photocatalysis for antibacterial activity and the binding of modified graphene oxide to wool fibers is weakened.

[0081] Comparison of Example 1 and Comparative Example 4 shows that when graphene oxide is replaced with nano-titanium dioxide, the functionality of the modified wool fabric is significantly reduced. This is because nano-titanium dioxide has relatively low far-infrared performance, antibacterial performance, and antistatic performance.

[0082] Comparing Example 1 and Comparative Example 5, it can be seen that when the various raw materials are simply mixed, the functionality and washability of the modified wool fabric are significantly reduced. This is because the graphene oxide cannot be effectively dispersed and has difficulty bonding with wool fibers, making the application of nano-graphene oxide on wool fibers difficult.

[0083] Comparing Example 1 and Comparative Example 6, it can be seen that the functionality and washability of the modified wool fabric are significantly reduced when the immersion temperature is adjusted to 60°C. This is because the scale layer on the surface of the wool fiber is difficult to open at this temperature, hindering the modified graphene oxide particles from entering the fiber interior. As a result, the modified graphene oxide is only adsorbed on the wool fiber surface. The nanographene oxide adsorbed on the wool fabric surface is easily removed by the soaping solution, resulting in poor washability of the modified wool fabric.

[0084] Comparing Example 1 and Comparative Example 7, it can be seen that when graphene oxide is not modified, the functionality and washability of the modified wool fabric are significantly reduced. This is because inorganic nanographene oxide has poor dispersibility in aqueous solutions and has difficulty bonding with wool fibers. This makes the application of nanographene oxide on wool fibers difficult and the preparation of durable, multifunctional wool fabrics challenging.

[0085] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A method for preparing a multifunctional wool fabric, characterized in that: The following steps are involved: S1, adding ethanolamine dropwise to the zinc nitrate solution to react and obtain zinc oxide sol; S2, adding baicalin to the zinc oxide sol described in S1 to react to obtain a composite sol; S3, adding graphene oxide to the composite sol described in S2 to react to obtain a modified graphene oxide dispersion; S4. Immersing the wool fabric in the modified graphene oxide dispersion described in S3 for finishing to obtain the multifunctional wool fabric.

2. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S1, the concentration of the zinc nitrate solution is 1 mol / L-2 mol / L; the solvent of the zinc nitrate solution is ethanol and ethylene glycol.

3. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S1, the molar ratio of zinc nitrate to ethanolamine is 1:(1.5-2.5); and the dropping speed of ethanolamine is 1 mL / min-1.5 mL / min.

4. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S1, the reaction temperature is 50°C-70°C, and the reaction time is 3h-5h.

5. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S2, the amount of baicalin used is 1 wt%-1.5 wt% of the zinc oxide sol.

6. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S2, the reaction temperature is 50°C-70°C, and the reaction time is 1.5h-3h.

7. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S3, the amount of graphene oxide used is 0.5wt%-1.5wt% of the composite sol.

8. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S3, the reaction is carried out at a pH of 6.5-7.5, a temperature of 50° C.-70° C., and a reaction time of 2 h-3 h.

9. The method for preparing the multifunctional wool fabric according to claim 1, characterized in that: In S4, the bath ratio of the immersion is 1:(20-40), the temperature is 90° C.-98° C., and the time is 40 min-70 min.

10. Multifunctional wool fabric prepared by the method according to any one of claims 1 to 9.

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