Antibacterial fabric finishing liquid containing halamine, antibacterial fabric as well as preparation method and application of antibacterial fabric
By forming Si-O-Si chemical bonds and silver ion bonds on the fabric surface, and combining nano-silver particles and carbon nanotubes, the problems of low antibacterial efficiency and decreased antibacterial ability after washing are solved, achieving a highly efficient and stable antibacterial effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- THE GBA NAT INST FOR NANOTECHNOLOGY INNOVATION
- Filing Date
- 2024-11-08
- Publication Date
- 2026-05-12
AI Technical Summary
Existing fabrics have low antibacterial efficiency, and their antibacterial ability decreases significantly after washing, affecting their mechanical properties.
A finishing solution containing haloamine siloxane derivatives and silver nitrate is used. By generating silanol compounds in an acidic aqueous solution, Si-O-Si chemical bonds are formed with the fabric surface. Silver ions are bonded to the fabric surface through in-situ ion exchange. Combined with nano-silver particles and carbon nanotubes, the antibacterial effect is improved.
It achieves highly efficient antibacterial performance, with a stable antibacterial rate, and can maintain a high level of antibacterial ability even after multiple washes.
Smart Images
Figure CN122013515A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of fabric finishing solution technology, and in particular to an antibacterial fabric finishing solution containing halogenated amines, antibacterial fabrics, their preparation methods and applications. Background Technology
[0002] In daily life, pathogens are usually spread through contact and multiply on surfaces. When pathogens multiply in large numbers and invade the human body through wounds or the mouth and nose, they will harm human health and even endanger life.
[0003] The structure of fabrics gives them a considerable surface area and the ability to absorb and retain moisture, which objectively makes them conducive to bacterial growth. Therefore, endowing textiles with antibacterial properties can effectively reduce bacterial growth on the fabric and reduce the chance of human contact with pathogens. Antibacterial fabrics are materials that inhibit the proliferation of surface bacteria, and are mainly divided into two categories: natural antibacterial textiles and synthetic antibacterial textiles. The raw materials of natural antibacterial textiles are mainly plant fibers in nature that have both strong antibacterial properties and linear macromolecular structures, such as bamboo fiber, hemp fiber, and seaweed fiber. Taking hemp fiber as an example, the flavonoids it contains have good antibacterial effects, and the hollow structure inside hemp fiber helps to inhibit the growth of anaerobic bacteria.
[0004] Artificial antibacterial textiles acquire their antibacterial properties by artificially adding antibacterial agents, such as quaternary ammonium salts, triclosan, biguanides, and metal salts, to the polymer surface. However, current methods of fabric treatment using incorporation or grafting of antibacterial agents generally suffer from low antibacterial efficiency and insufficient antibacterial ability after washing. Furthermore, directly incorporating antibacterial agents into textiles may affect the material's mechanical properties. Summary of the Invention
[0005] This invention provides an antibacterial fabric finishing solution containing halogenated amines, an antibacterial fabric, a preparation method thereof, and its application, in order to solve the technical problems of low antibacterial efficiency or significant decrease in antibacterial ability after washing in current fabrics.
[0006] To address the aforementioned technical problems, one objective of this invention is to provide a halogen amine antibacterial fabric finishing solution, comprising an organic solution containing an antibacterial halogen amine siloxane derivative accounting for 8-15 vol% of the finishing liquid volume, silver nitrate at a concentration of 0.1-0.5 mol / L, and the balance being water;
[0007] The concentration of the antibacterial halogenated siloxane derivative in the organic solution containing the antibacterial halogenated siloxane derivative is 200-400 g / L, and the structural formula of the antibacterial halogenated siloxane derivative is as follows:
[0008] In the antibacterial fabric finishing solution provided in this application, silver nitrate ionizes into hydrogen ions in water, making the aqueous solution acidic. The siloxane of the antibacterial silane derivative containing halogen amine undergoes a hydrolysis reaction in the acidic aqueous solution to generate silanol compounds. The hydroxyl groups contained therein can undergo a dehydration condensation reaction with the hydroxyl groups on the fabric surface to generate strong Si-O-Si chemical bonds. This allows the halogen amine groups to be stably modified on the fabric surface to provide broad-spectrum and highly efficient antibacterial effects. At the same time, silver ions in the solution can replace the carboxyl groups on the fabric surface using an in-situ ion exchange method, resulting in silver ions bonded to the fabric surface. Silver ions can destroy the DNA molecular structure of bacteria, providing antibacterial effects. Through the synergistic antibacterial action of halogen amine and silver ions on the fabric surface, a high antibacterial rate is achieved, and the antibacterial rate of the fabric remains high even after washing.
[0009] As a preferred embodiment, the organic solvent in the organic solution containing the antibacterial haloamine siloxane derivative is N,N-dimethylformamide.
[0010] As a preferred embodiment, the preparation method of the antibacterial haloamine siloxane derivative includes the following steps:
[0011] (1) Dissolve 5,5-dimethylhydantoin and sodium hydroxide in a solvent, stir until completely dissolved, and distill under reduced pressure until the solvent evaporates completely to obtain sodium 5,5-dimethylhydantoin.
[0012] (2) Dissolve 5,5-dimethylhydantoin sodium salt in an organic solvent and stir to dissolve. Add 3-chloropropyltriethoxysilane slowly dropwise into a syringe. After the reaction is complete, filter to remove insoluble matter to obtain an N,N-dimethylformamide solution containing antibacterial haloamine siloxane derivatives.
[0013] As a preferred embodiment, in step (1) of the method for preparing the antibacterial halogenated siloxane derivative, the molar ratio of 5,5-dimethylhydantoin to sodium hydroxide is 1:(1-1.05).
[0014] As a preferred embodiment, in step (1) of the preparation method of the antibacterial halogen amine siloxane derivative, 1 mol of the 5,5-dimethylhydantoin is added to 500-1000 mL of solvent A.
[0015] As a preferred embodiment, in step (1) of the preparation method of the antibacterial halogen amine siloxane derivative, the solvent is anhydrous ethanol.
[0016] As a preferred embodiment, in step (2) of the method for preparing the antibacterial haloamine siloxane derivative, the molar ratio of 5,5-dimethylhydantoin sodium salt and 3-chloropropyltriethoxysilane is (1-1.5):1.
[0017] As a preferred embodiment, in step (2) of the preparation method of the antibacterial halogenated siloxane derivative, 1 mol of the 5,5-dimethylhydantoin sodium salt is added to 500-1000 mL of organic solvent.
[0018] As a preferred embodiment, in step (2) of the method for preparing the antibacterial halogen amine siloxane derivative, the syringe advance rate is 0.08 mm / min.
[0019] As a preferred embodiment, in step (2) of the preparation method of the antibacterial halogen amine siloxane derivative, the reaction temperature is 80-100℃ and the reaction time is 3-6 hours.
[0020] To address the aforementioned technical problems, a second objective of this invention is to provide an application of a halogenated amine antibacterial fabric finishing solution in the preparation of antibacterial fabrics.
[0021] To address the aforementioned technical problems, a third objective of this invention is to provide a method for preparing an antibacterial fabric containing halogenated amines, comprising the following steps:
[0022] (1) Immerse the textile in a fabric finishing solution, heat it to react, and then remove it;
[0023] (2) Immerse the textile completely in a dimethylamine borane aqueous solution, let it stand to react, and then remove it;
[0024] (3) The textile is baked and dried to obtain an antibacterial fabric containing halogen amines.
[0025] In this application, when the fabric is immersed in a fabric finishing solution, the siloxane of the antibacterial silane derivative containing halogen amines in the finishing solution is hydrolyzed into silanol compounds. The hydroxyl groups contained therein can react with the hydroxyl groups on the fabric surface to dehydrate, thereby making the halogen amine groups stably modified on the fabric surface to provide a broad-spectrum and highly efficient antibacterial effect. At the same time, the silver ions in the solution can replace the hydrogen ions on the carboxyl groups on the fabric surface, so that silver ions are bonded on the fabric surface. Dimethylamine borane is used to reduce the silver ions on the fabric to nano-silver particles, which have higher water washing antibacterial stability. Through the synergistic antibacterial effect of halogen amines and nano-silver particles on the fabric surface, a high antibacterial rate is achieved, and the antibacterial rate of the fabric remains high after water washing.
[0026] As a preferred embodiment, in step (2), the textile is completely immersed in an aqueous solution of dimethylamine borane and allowed to stand for reaction. After being removed, the textile is completely immersed in an organic solution containing amino carbon nanotubes, heated to complete the reaction, and then removed.
[0027] When the fabric of this application is immersed in an organic solution containing amino carbon nanotubes, the amino groups on the amino carbon nanotubes can react with the carboxyl groups on the fabric to generate stable amide compounds on the fabric surface, thereby making the carbon nanotubes stably bound to the fabric surface. The hollow tubular structure of the carbon nanotubes can destroy the bacterial cell wall through mechanical action, thereby further improving the antibacterial efficiency of the fabric.
[0028] As a preferred embodiment, in step (1), the heating reaction temperature is 100-120℃ and the reaction time is 30-120min.
[0029] As a preferred embodiment, in step (2), the concentration of dimethylamine borane in the aqueous solution of dimethylamine borane is 0.01-0.05 mol / L.
[0030] As a preferred option, in step (2), the reaction time is 5-30 min.
[0031] As a preferred embodiment, in step (2), the concentration of amino carbon nanotubes in the organic solution containing amino carbon nanotubes is 0.2-0.4 mol / L.
[0032] As a preferred embodiment, in step (3), the baking temperature is 100-120℃ and the baking time is 30-120℃.
[0033] As a preferred embodiment, the organic solution containing amino carbon nanotubes contains sulfuric acid with a concentration of 0.01-0.02 mol / L, and the diameter of the amino carbon nanotubes is 1-10 nm.
[0034] To address the aforementioned technical problems, the fourth objective of this invention is to provide a method for preparing antibacterial fabrics containing halogenated amines.
[0035] As a preferred embodiment, the textile is made of renewable natural fibers.
[0036] As a preferred embodiment, the textile is made of at least one of cotton, wool, silk, and linen.
[0037] Compared with the prior art, the present invention has the following beneficial effects:
[0038] 1. In the antibacterial fabric finishing solution of this application, the antibacterial silane derivative containing halogen amines undergoes a hydrolysis reaction in an acidic aqueous solution to generate silanol compounds. The hydroxyl groups contained therein can undergo a dehydration condensation reaction with the hydroxyl groups on the fabric surface to form a strong Si-O-Si chemical bond, thereby enabling the halogen amine groups to be stably modified on the fabric surface to provide a broad-spectrum and highly efficient antibacterial effect. Silver ions can replace the hydrogen ions of the carboxyl groups on the fabric surface, so that silver ions are bonded on the fabric surface. Through the synergistic antibacterial effect of halogen amines and silver ions on the fabric surface, a high antibacterial rate is achieved, and the antibacterial rate of the fabric remains at a high level after washing.
[0039] 2. In the preparation process of the antibacterial fabric of this application, silver ions in the finishing solution can be bonded to the surface of the fabric. Dimethylamine borane is used to reduce the silver ions bonded to the fabric into nano-silver particles, which have higher water washing antibacterial stability. Through the synergistic antibacterial effect of haloamine and nano-silver particles on the fabric surface, a high antibacterial rate is achieved.
[0040] 3. When the fabric of this application is immersed in an organic solution containing amino carbon nanotubes, the amino groups on the amino carbon nanotubes can react with the carboxyl groups on the fabric to generate stable amide compounds on the fabric surface, thereby making the carbon nanotubes stably bound to the fabric surface. The hollow tubular structure of the carbon nanotubes can destroy the bacterial cell wall through mechanical action, thereby further improving the antibacterial efficiency of the fabric. Moreover, the antibacterial rate is stable and high, and can be maintained after washing. Attached Figure Description
[0041] Figure 1 : This refers to the reaction process in the preparation of antibacterial haloamine siloxane derivatives in the embodiments and comparative examples of the present invention;
[0042] Figure 2 This invention relates to the chemical reaction process of the antibacterial haloamine siloxane derivative, in which the siloxane reacts with the hydroxyl groups on the surface of textiles.
[0043] Figure 3 This invention describes the chemical reaction process by which silver nitrate is loaded onto the surface of a fabric and reduced to nano-silver particles via in-situ ion exchange. Detailed Implementation
[0044] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. 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 skilled in the art without creative effort are within the scope of protection of the present invention.
[0045] Unless otherwise specified, the test methods used in the following embodiments of this application are conventional methods; and the materials and reagents used are commercially available unless otherwise specified.
[0046] Amino-carbon nanotubes, specifically the XFS14 model from Xianfeng Nano, with a diameter of 1-2 nm.
[0047] Example 1
[0048] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (15 vol%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.2 mol / L AgNO3, and the balance water, wherein the concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 250 g / L, and the structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution includes the following steps:
[0049] (1) In a reactor equipped with an electric stirrer, add 0.5 mol / L 5,5-dimethylhydantoin and 0.5 mol / L flake sodium hydroxide, dissolve in 1000 mL of anhydrous ethanol, stir for 1 hour until completely dissolved, connect the reactor to a vacuum distillation apparatus, and distill under reduced pressure until the solvent has completely evaporated, leaving white crystalline 5,5-dimethylhydantoin sodium salt. The reaction equation is as follows: Figure 1 As shown;
[0050] (2) In a reactor equipped with an electric stirrer, a reflux condenser, and a heating device, add 0.5 mol of 5,5-dimethylhydantoin sodium salt and 500 mL of N,N-dimethylformamide, stir to dissolve, and take 0.5 mol of 3-chloropropyltriethoxysilane into a 200 mL syringe, connect a syringe pump, and slowly add it dropwise into the reactor at a rate of 0.13 mm / min. Raise the reaction temperature to 90 °C and react for 6 hours. Filter the reaction solution to remove sodium chloride insoluble matter to obtain an N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives. Adjust the concentration of the antibacterial halogenated siloxane derivatives to 250 g / L. The reaction equation for the antibacterial halogenated siloxane derivatives is as follows: Figure 1 As shown;
[0051] (3) Mix 150 mL of N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives with some water, add silver nitrate solid, dilute with water to 1000 mL, stir until fully dissolved and dispersed, the concentration of silver nitrate is 0.2 mol / L, and the finishing solution is obtained.
[0052] Example 2
[0053] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.1 mol / L AgNO3, and the balance being water. The N,N-dimethylformamide solution contains an antibacterial halogenated amine siloxane derivative with a concentration of 300 g / L. The structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution includes the following steps:
[0054] (1) In a reactor equipped with an electric stirrer, add 0.3 mol / L of 5,5-dimethylhydantoin and 0.3 mol / L of flake sodium hydroxide, dissolve in 250 mL of anhydrous ethanol, stir for 1 hour until completely dissolved, connect the reactor to a vacuum distillation apparatus, and distill under reduced pressure until the solvent has completely evaporated, leaving white crystalline 5,5-dimethylhydantoin sodium salt. The reaction equation is as follows: Figure 1 As shown;
[0055] (2) In a reactor equipped with an electric stirrer, a reflux condenser, and a heating device, add 0.3 mol of 5,5-dimethylhydantoin sodium salt and 250 mL of N,N-dimethylformamide, stir to dissolve, and take 0.3 mol of 3-chloropropyltriethoxysilane into a 100 mL syringe, connect a syringe pump, and slowly add it dropwise into the reactor at a rate of 0.08 mm / min. Raise the reaction temperature to 95°C and react for 4 hours. Filter the reaction solution to remove sodium chloride insoluble matter, obtaining an N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives. Adjust the concentration of the antibacterial halogenated siloxane derivatives to 300 g / L. The reaction equation for the antibacterial halogenated siloxane derivatives is as follows: Figure 1 As shown;
[0056] (3) Mix 100 mL of N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives with some water, add silver nitrate solid, dilute with water to 1000 mL, stir until fully dissolved and dispersed, the concentration of silver nitrate is 0.1 mol / L, and the finishing solution is obtained.
[0057] Example 3
[0058] An antibacterial fabric finishing solution containing halogenated amines, comprising, in the following raw materials: an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative (8 vt% of the finishing liquid volume), AgNO3 at a concentration of 0.1 mol / L, and the balance being water; the concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 350 g / L; and the structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution includes the following steps:
[0059] (1) In a reactor equipped with an electric stirrer, add 1 mol of 5,5-dimethylhydantoin and 1 mol of flake sodium hydroxide, dissolve them in 1000 mL of anhydrous ethanol, stir for 2 hours until completely dissolved, connect the reactor to a vacuum distillation apparatus, and distill under reduced pressure until the solvent has completely evaporated, leaving white crystalline 5,5-dimethylhydantoin sodium salt. The reaction equation is as follows: Figure 1 As shown;
[0060] (2) In a reactor equipped with an electric stirrer, a reflux condenser, and a heating device, add 1 mol of 5,5-dimethylhydantoin sodium salt and 1000 mL of N,N-dimethylformamide, stir to dissolve, and take 1 mol of 3-chloropropyltriethoxysilane into a 500 mL syringe, connect a syringe pump, and slowly add it dropwise into the reactor at a rate of 0.2 mm / min. Raise the reaction temperature to 95°C and react for 6 hours. Filter the reaction solution to remove sodium chloride insoluble matter, obtaining an N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives. Adjust the concentration of the antibacterial halogenated siloxane derivatives to 350 g / L. The reaction equation for the antibacterial halogenated siloxane derivatives is as follows: Figure 1 As shown;
[0061] (3) Mix 80 mL of N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives with some water, add silver nitrate solid, dilute with water to 1000 mL, stir until fully dissolved and dispersed, the concentration of silver nitrate is 0.1 mol / L, and the finishing solution is obtained.
[0062] Example 4
[0063] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.2 mol / L AgNO3, and the balance water, wherein the concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 300 g / L, and the structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (3), 100 mL of N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivative is mixed with some water, silver nitrate solid is added, and the volume is adjusted to 1000 mL with water. The mixture is stirred until fully dissolved and dispersed, and the concentration of silver nitrate is 0.2 mol / L to obtain the finishing solution.
[0064] Example 5
[0065] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.5 mol / L AgNO3, and the balance water, wherein the concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 300 g / L, and the structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (3), 100 mL of N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivative is mixed with some water, silver nitrate solid is added, and the volume is adjusted to 1000 mL with water. The mixture is stirred until fully dissolved and dispersed, and the concentration of silver nitrate is 0.5 mol / L to obtain the finishing solution.
[0066] Example 6
[0067] An antibacterial fabric finishing solution containing halogenated amines comprises, by means of 10 vol% N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.1 mol / L AgNO3, and the balance being water. The concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 200 g / L. The structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (2), 0.3 mol of 5,5-dimethylhydantoin sodium salt and 250 mL of N,N-dimethylformamide are added to a reactor equipped with an electric stirring device, a reflux condenser and a heating device, stirred and dissolved, and 0.3 mol of 3-chloropropyltriethoxysilane is put into a 100 mL syringe, connected to a syringe pump, and slowly added dropwise to the reactor at a rate of 0.08 mm / min. The reaction temperature is raised to 95°C and the reaction is carried out for 4 hours. The reaction solution is filtered to remove sodium chloride insoluble matter to obtain an N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivatives. The concentration of the antibacterial halogen amine siloxane derivatives is adjusted to 200 g / L.
[0068] Example 7
[0069] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.5 mol / L AgNO3, and the balance water, wherein the concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 200 g / L, and the structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (2), 0.3 mol of 5,5-dimethylhydantoin sodium salt and 250 mL of N,N-dimethylformamide are added to a reactor equipped with an electric stirring device, a reflux condenser and a heating device, stirred and dissolved, and 0.3 mol of 3-chloropropyltriethoxysilane is put into a 100 mL syringe, connected to a syringe pump, and slowly added to the reactor at a rate of 0.08 mm / min. The reaction temperature is raised to 95°C and the reaction is carried out for 4 hours. The reaction solution is filtered to remove sodium chloride insoluble matter to obtain an N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivatives. The concentration of the antibacterial halogen amine siloxane derivatives is adjusted to 200 g / L.
[0070] In step (3), 100 mL of N,N-dimethylformamide solution containing antibacterial halogenated siloxane derivatives is mixed with some water, silver nitrate solid is added, and the volume is adjusted to 1000 mL with water. The mixture is stirred until fully dissolved and dispersed, and the concentration of silver nitrate is 0.5 mol / L, thus obtaining the finishing solution.
[0071] Comparative Example 1
[0072] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.1 mol / L HNO3, and the balance being water. The concentration of the antibacterial halogenated amine siloxane derivative in the N,N-dimethylformamide solution is 300 g / L. The structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (3), 100 mL of N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivative is mixed with some water, 0.1 mol of nitric acid is added, and the volume is adjusted to 1000 mL with water to obtain the finishing solution.
[0073] Comparative Example 2
[0074] An antibacterial fabric finishing solution is prepared by means of N,N-dimethylformamide solution (10 wt% of the finishing liquid volume), AgNO3 (0.1 mol / L concentration), and the remainder water. The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2, except that in step (3), 100 mL of N,N-dimethylformamide solution is mixed with some water, silver nitrate solid is added, and the volume is adjusted to 1000 mL with water. The mixture is stirred until fully dissolved and dispersed, and the concentration of silver nitrate is 0.1 mol / L, thus obtaining the finishing solution.
[0075] Comparative Example 3
[0076] An antibacterial fabric finishing solution containing halogenated amines, comprising, by weight (10 wt%), an N,N-dimethylformamide solution containing an antibacterial halogenated amine siloxane derivative, 0.1 mol / L AgNO3, and the balance being water. The N,N-dimethylformamide solution contains an antibacterial halogenated amine siloxane derivative with a concentration of 100 g / L. The structural formula of the antibacterial halogenated amine siloxane derivative is as follows: The preparation method of the antibacterial fabric finishing solution is the same as that in Example 2, with the same reagents, equipment and process parameters. The difference is that in step (2), 0.3 mol of 5,5-dimethylhydantoin sodium salt and 250 mL of N,N-dimethylformamide are added to a reactor equipped with an electric stirrer, a reflux condenser and a heating device. The mixture is stirred and dissolved. 0.3 mol of 3-chloropropyltriethoxysilane is placed in a 100 mL syringe, connected to a syringe pump, and slowly added dropwise to the reactor at a rate of 0.08 mm / min. The reaction temperature is raised to 95°C and the reaction is carried out for 4 hours. The reaction solution is filtered to remove sodium chloride insoluble matter, and an N,N-dimethylformamide solution containing antibacterial halogen amine siloxane derivative is obtained. The concentration of the antibacterial halogen amine siloxane derivative is adjusted to 100 g / L.
[0077] Application Example 1
[0078] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0079] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 1, and take it out after reacting at a temperature of 120°C for 60 minutes;
[0080] (2) Dissolve 0.05 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.05 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0081] (3) Dissolve 0.3 mol of amino carbon nanotubes in 1 L of N,N-dimethylformamide. The amino carbon nanotubes are XFS14 from Xianfeng Nano, with a diameter of 1-2 nm. At the same time, add 0.01 mol of sulfuric acid to prepare an N,N-dimethylformamide solution containing amino carbon nanotubes. Completely immerse the textile square towel in the N,N-dimethylformamide solution containing amino carbon nanotubes, heat to 160°C, let stand for about 3 hours, and then take it out.
[0082] (4) The textile square towel is baked and dried at 100°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0083] Application Example 2
[0084] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0085] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 2, react at a temperature of 110°C for 90 minutes, and then take it out;
[0086] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0087] (3) Dissolve 0.2 mol of amino carbon nanotubes in 1 L of N,N-dimethylformamide. The amino carbon nanotubes are XFS14 from Xianfeng Nano, with a diameter of 1-2 nm. At the same time, add 0.01 mol of sulfuric acid to prepare an N,N-dimethylformamide solution containing amino carbon nanotubes. Completely immerse the textile square towel in the N,N-dimethylformamide solution containing amino carbon nanotubes, heat to 160°C, let stand for about 3 hours, and then take it out.
[0088] (4) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0089] Application Example 3
[0090] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0091] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 3, react at 100°C for 60 minutes and then take it out;
[0092] (2) Dissolve 0.08 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.08 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0093] (3) Dissolve 0.1 mol of amino carbon nanotubes in 1 L of N,N-dimethylformamide. The amino carbon nanotubes are XFS14 from Xianfeng Nano, with a diameter of 1-2 nm. At the same time, add 0.01 mol of sulfuric acid to prepare an N,N-dimethylformamide solution containing amino carbon nanotubes. Completely immerse the textile square towel in the N,N-dimethylformamide solution containing amino carbon nanotubes, heat to 160°C, let stand for about 3 hours, and then take it out.
[0094] (4) The textile square towel is baked and dried at 110°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0095] Application Example 4
[0096] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters used in each step. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Example 4 and taken out after reacting for 60 minutes.
[0097] Application Example 5
[0098] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters used in each step. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Example 5 and taken out after reacting for 60 minutes.
[0099] Application Example 6
[0100] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters used in each step. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Example 6 and taken out after reacting for 60 minutes.
[0101] Application Example 7
[0102] An antibacterial fabric containing halogen amines is prepared in the same way as Example 2, with the same steps, reagents, equipment and process parameters. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Example 7 and taken out after reacting for 60 minutes.
[0103] Application Example 8
[0104] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0105] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 1, react at a temperature of 110°C for 90 minutes, and then take it out;
[0106] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0107] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0108] Application Example 9
[0109] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0110] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 2, react at a temperature of 110°C for 90 minutes, and then take it out;
[0111] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0112] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0113] Application Example 10
[0114] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0115] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 3, react at a temperature of 110°C for 90 minutes, and then take it out;
[0116] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0117] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0118] Application Example 11
[0119] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0120] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 4, and take it out after reacting at a temperature of 110°C for 90 minutes;
[0121] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0122] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0123] Application Example 12
[0124] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0125] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 5, react at a temperature of 110°C for 90 minutes, and then take it out;
[0126] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0127] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0128] Application Example 13
[0129] An antibacterial fabric, the preparation method of which includes the following steps:
[0130] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 2, react at a temperature of 110°C for 90 minutes, and then take it out;
[0131] (2) Dissolve 0.2 mol of amino carbon nanotubes in 1 L of N,N-dimethylformamide, and add 0.01 mol of sulfuric acid at the same time. The amino carbon nanotubes are XFS14 from Xianfeng Nano, with a diameter of 1-2 nm. Prepare an N,N-dimethylformamide solution containing amino carbon nanotubes. Completely immerse the textile square towel in the N,N-dimethylformamide solution containing amino carbon nanotubes, heat to 160°C, let stand for about 3 hours, and then take it out.
[0132] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0133] Comparative Application Example 1
[0134] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters used in each step. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Comparative Example 1 and taken out after reacting for 60 minutes.
[0135] Comparative Application Example 2
[0136] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Comparative Example 2 and taken out after reacting for 60 minutes.
[0137] Comparative Application Example 3
[0138] The preparation method of an antibacterial fabric containing halogen amines is the same as that of Application Example 2 in terms of each step, reagents, equipment and process parameters used in each step. The difference is that in step (1), the cotton fiber textile square towel is soaked in the fabric finishing solution of Comparative Example 3 and taken out after reacting for 60 minutes.
[0139] Comparative Application Example 4
[0140] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0141] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 6, react at a temperature of 110°C for 90 minutes, and then take it out;
[0142] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0143] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0144] Comparative Application Example 5
[0145] A halogenated amine-containing antibacterial fabric, the preparation method of which includes the following steps:
[0146] (1) Soak the cotton fiber textile square towel in the fabric finishing solution of Example 7, and take it out after reacting for 90 minutes;
[0147] (2) Dissolve 0.1 mol of dimethylamine borane in 1 L of water to prepare a dimethylamine borane solution with a concentration of 0.1 mol / L. Completely immerse the textile handkerchief in the dimethylamine borane solution, let it stand for about 10 minutes, and then take it out.
[0148] (3) The textile square towel is baked and dried at 120°C for 2 hours to obtain an antibacterial fabric square towel containing halogen amine.
[0149] Performance testing
[0150] The fabric handkerchiefs prepared in the application examples or comparative application examples were machine washed three times and then dried. The antibacterial properties of the fabric handkerchiefs before and after the three machine washes were tested using the film antibacterial method.
[0151] Film-coated antibacterial method: Inoculate Escherichia coli (E. coli) or Staphylococcus aureus (S. aureus) onto nutrient agar slant and incubate at 37°C for 24 hours. Using an inoculation loop, scrape 1-2 loops from the culture medium and add a small amount of fresh bacteria to the culture medium, making a 10-fold dilution (102). -1 ) or 100 times diluted (10 -2 ), to obtain the inoculum; according to GB / T4789.2 standard, take 0.5 mL of 10 -1 10 -2 The inoculum was dropped onto the negative control plate, the blank control plate, and the plate containing the application example or comparison application example fabric square. Sterile forceps were used to pick up the sterile covering film and cover the corresponding sample, ensuring it was flat and free of air bubbles, so that the inoculum was evenly in contact with the sample. The plate was then placed in a sterile Petri dish and incubated for 24 hours at (37±1)℃ and relative humidity >90%. Three parallel experiments were performed for each concentration of inoculum. After 24 hours of incubation, 20 mL of washing buffer was added to each sample, and the sample was repeatedly washed and covered with the film. After thorough mixing, the washing buffer was inoculated into nutrient agar medium and incubated for 24 hours at (37±1)℃. The viable bacteria were counted, and the number of viable bacteria in the washing buffer was counted according to GB / T 4789.2. The statistical results are shown in Table 1 below.
[0152] Table 1 - Antibacterial test results of fabric handkerchiefs before and after washing in the application examples and comparative application examples of this application.
[0153]
[0154]
[0155] As shown in Table 1, a comparison between Application Example 2 and Comparative Application Examples 1-2 reveals that the preparation of antibacterial silane derivatives using 5,5-dimethylhydantoin and 3-chloropropyltriethoxysilane yields... Figure 2 As shown, this antibacterial silane derivative undergoes hydrolysis in acidic aqueous solution to generate silanol compounds. The hydroxyl groups in these compounds can undergo dehydration condensation with the hydroxyl groups of fabric fibers to form strong Si-O-Si chemical bonds, allowing the haloamine groups to be stably modified onto the fabric fibers. This haloamine then releases hypohalous acid through a reaction with water to achieve its antibacterial effect. It has advantages such as rapid onset of action, broad antibacterial spectrum, regenerable resistance, and no biological or environmental toxicity. Furthermore, as... Figure 3As shown, silver ions in the finishing solution replace hydrogen ions of the carboxyl groups in the fabric fibers through in-situ ion exchange, thereby enabling the fabric to carry silver ions. Subsequently, dimethylamine borane is used to reduce the silver ions on the fabric into chemically stable and highly antibacterial nanoparticles. The nanoparticles can deform the DNA molecular structure of bacteria, thus inactivating them. The method in Application Example 2 of this application, by modifying the fabric with halogenated amine groups and carrying nanoparticles, can combine to improve the bactericidal effect of the fabric, achieving a high antibacterial rate, and the antibacterial rate of the fabric remains at a high level after washing. In contrast, the fabric in Comparative Application Example 1 was not modified with halogenated amine groups, and the fabric in Comparative Application Example 2 did not carry nanoparticles, resulting in insufficient antibacterial rate.
[0156] As shown in Table 1, by comparing the schemes in Examples 2 and 4-5, it can be seen that as the concentration of silver nitrate in the finishing solution increases, the antibacterial activity of the prepared fabric against Escherichia coli and Staphylococcus aureus first increases and then remains stable. This indicates that the concentration of silver ions that exchange with hydrogen ions of hydroxyl groups in the fabric in the 0.2-0.5 mol / L silver nitrate solution has reached its maximum, and the ability to improve the antibacterial rate of the fabric is limited.
[0157] As shown in Table 1, a comparison of the solutions in Application Examples 2, 6-7, and Comparative Application Example 3 reveals that the finishing solution in Application Examples 6-7 contains a lower content of antibacterial haloamine siloxane derivatives, resulting in a lower content of modified haloamines on the fabric. This leads to lower inhibition efficiency against bacterial growth and reproduction, resulting in a significant decrease in the fabric's antibacterial rate. Meanwhile, a comparison of the solutions in Application Example 2 and Comparative Application Examples 4-5 shows that this application introduces carbon nanotubes into the fabric by reacting the amino groups of amino carbon nanotubes with the carboxyl groups on the fabric to generate stable amide compounds. These carbon nanotubes not only possess good chemical stability, but their hollow tubular structure can also mechanically disrupt bacterial cell walls, thereby improving the fabric's antibacterial efficiency.
[0158] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the scope of protection of the present invention. In particular, it should be noted that any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention for those skilled in the art.
Claims
1. A halogenated amine antibacterial fabric finishing solution, characterized in that, It includes an organic solution containing antibacterial haloamine siloxane derivatives, comprising 8-15% of the liquid component, silver nitrate at a concentration of 0.1-0.5 mol / L, and the remainder being water; The concentration of the antibacterial halogenated siloxane derivative in the organic solution containing the antibacterial halogenated siloxane derivative is 200-400 g / L, and the structural formula of the antibacterial halogenated siloxane derivative is as follows:
2. The halogenated amine antibacterial fabric finishing solution as described in claim 1, characterized in that, The organic solvent in the organic solution containing the antibacterial haloamine siloxane derivative is N,N-dimethylformamide.
3. The halogenated amine antibacterial fabric finishing solution as described in claim 1, characterized in that, The preparation method of the antibacterial haloamine siloxane derivative includes the following steps: (1) Dissolve 5,5-dimethylhydantoin and sodium hydroxide in a solvent, stir until completely dissolved, and distill under reduced pressure until the solvent evaporates completely to obtain sodium 5,5-dimethylhydantoin. (2) Dissolve 5,5-dimethylhydantoin sodium salt in an organic solvent and stir to dissolve. Add 3-chloropropyltriethoxysilane slowly dropwise into a syringe. After the reaction is complete, filter to remove insoluble matter to obtain an N,N-dimethylformamide solution containing antibacterial haloamine siloxane derivatives.
4. The halogenated amine antibacterial fabric finishing solution as described in claim 1, characterized in that, In the method for preparing the antibacterial haloamine siloxane derivative, at least one of the following (a)-g) is satisfied: a) In step (1), the molar ratio of 5,5-dimethylhydantoin to sodium hydroxide is 1:(1-1.05); b) In step (1), 1 mol of the 5,5-dimethylhydantoin is added to 500-1000 mL of solvent A; c) In step (1), the solvent is anhydrous ethanol; d) In step (2), the molar ratio of the 5,5-dimethylhydantoin sodium salt and the 3-chloropropyltriethoxysilane is (1-1.5):1; e) In step (2), 1 mol of the 5,5-dimethylhydantoin sodium salt is added to 500-1000 mL of organic solvent; (f) In step (2), the syringe advance rate is 0.08 mm / min; (g) In step (2), the reaction temperature is 80-100℃ and the reaction time is 3-6 hours.
5. The use of the halogen amine antibacterial fabric finishing solution as described in any one of claims 1-4 in the preparation of antibacterial fabrics.
6. A method for preparing an antibacterial fabric containing halogenated amines, characterized in that, The method of using the halogen amine antibacterial fabric finishing solution as described in any one of claims 1-4 includes the following steps: (1) Immerse the textile in a fabric finishing solution, heat it to react, and then remove it; (2) Immerse the textile completely in a dimethylamine borane aqueous solution, let it stand to react, and then remove it; (3) The textile is baked and dried to obtain an antibacterial fabric containing halogen amines.
7. The method for preparing a halogenated amine-containing antibacterial fabric as described in claim 6, characterized in that, In step (2), the textile is completely immersed in an aqueous solution of dimethylamine borane and allowed to stand for reaction. After being removed, the textile is completely immersed in an organic solution containing amino carbon nanotubes and heated until the reaction is complete. Then it is removed.
8. The method for preparing a halogenated amine-containing antibacterial fabric as described in claim 7, characterized in that, Satisfying at least one of the following a)-e): a) In step (1), the heating reaction temperature is 100-120℃ and the reaction time is 30-120 min; b) In step (2), the concentration of dimethylamine borane in the aqueous solution of dimethylamine borane is 0.01-0.05 mol / L; c) In step (2), the reaction time is 5-30 min; d) In step (2), the concentration of amino carbon nanotubes in the organic solution containing amino carbon nanotubes is 0.2-0.4 mol / L; e) In step (3), the baking temperature is 100-120℃ and the baking time is 30-120℃.
9. The method for preparing a halogenated amine-containing antibacterial fabric as described in claim 7, characterized in that, The organic solution containing amino carbon nanotubes contains sulfuric acid at a concentration of 0.01-0.02 mol / L, and the diameter of the amino carbon nanotubes is 1-10 nm.
10. A method for preparing a halogenated amine-containing antimicrobial fabric according to any one of claims 6-9, resulting in an antimicrobial fabric containing halogenated amines.