Photosensitive antibacterial down and its preparation and application

Abstract

The present invention relates to a kind of photosensitive antibacterial down and its preparation and application, the preparation method comprises the following steps: dissolving chitosan in acetic acid solution to prepare chitosan solution, adding pretreated down to glutaraldehyde aqueous solution, then adding chitosan solution, carrying out cross-linking reaction, and obtaining down cross-linked with chitosan; using 2,2'-hydroxy-4-methoxybenzophenone, and any two of copper, nickel, and zinc metal salts as raw materials to prepare a bimetallic coordinated loaded benzophenone photosensitizer; activating the loaded benzophenone photosensitizer; impregnating the down cross-linked with chitosan in the activated loaded benzophenone photosensitizer, carrying out condensation reaction, and obtaining photosensitive antibacterial down. The photosensitive antibacterial down prepared by the present invention has long-lasting antibacterial property, and has a wide antibacterial range, high safety, high antibacterial efficiency, and high photodynamic efficiency. The preparation method of the present invention has mild reaction conditions, low energy consumption, simple process, and is easy to industrialize.

Description

Technical Field

[0001] The present application relates to the field of textile processing technology, and in particular to a photosensitive antibacterial down and its preparation and application. Background Art

[0002] Down is chemically composed of protein and animal fat. Even repeated degreasing and washing cannot completely eliminate impurities and bacteria. Furthermore, down contains numerous stains and pathogenic microorganisms. If down processing is not properly sterilized, down products will harbor a large number of pathogens, posing a health risk. Furthermore, down products are inevitably exposed to the long-term effects of heat and humidity during wear and storage, significantly increasing the risk of mold and odor, which can pose a health risk. This can also severely reduce the warmth and loft of down, negating the inherent advantages of down products. Therefore, developing antimicrobial properties in down is highly applicable and of great significance.

[0003] The existing production process for antibacterial down includes the following steps: pre-sorting, ash removal, fine sorting, washing, dehydration, finishing, drying, cooling, and packaging. Traditional down antibacterial finishing uses a series of chemicals, such as trichloroisocyanuric acid, to treat the down during the drying process. Trichloroisocyanuric acid is a strong oxidizing and chlorinating agent with a strong chlorine odor. The treated down exhibits poor loft and significant down performance degradation. The process also poses a significant environmental risk, and the antibacterial properties of down products are almost completely lost after two washes.

[0004] Photodynamic antimicrobial technology inactivates bacteria by generating toxic reactive oxygen species (ROS) when photosensitizers are stimulated by visible light. These ROS can diffuse within a certain range, inactivating bacteria without contact. Photodynamic antimicrobial technology does not induce bacterial resistance, thus addressing the shortcomings of antibiotics. Its bacterial killing effect can also be enhanced by the photochemical synergy of inorganic salts, making it a highly effective new technology for sterilization.

[0005] Existing research has been conducted on adding photosensitizers to down to increase its antibacterial properties, but the photosensitizers used tend to be natural photosensitizers such as coumarin. For example, patent publication number CN113638233B discloses a method for deodorizing duck down, which includes the following steps: (1) pretreatment: washing the duck down to remove dust or impurities attached to the surface; (2) double degreasing: soaking the washed and dried duck down in warm alkaline water for the first degreasing step, then soaking the duck down in warm water and adding a complex enzyme to the warm water for the second degreasing step; (3) sterilization: dehydrating and drying the duck down after step (2), spraying it with photosensitizer, and then performing ultraviolet sterilization; (4) drying and storage: soaking the sterilized duck down again to remove residual substances, dehydrating and drying it, and then sending it to a down bin for storage. Through double degreasing, the fishy smell of duck down is significantly removed, and by adding photosensitizers during ultraviolet sterilization, rapid sterilization is achieved. Compared with ultraviolet lamp sterilization, the treatment time is short, and the antibacterial and antibacterial functions are increased in the duck down.

[0006] However, the natural photosensitizers used in the above scheme have a limited wavelength range. The light wavelength required by the natural photosensitizers can easily cause damage to normal cells. At the same time, the natural photosensitizers cannot take into account both antibacterial effects and selectivity for bacteria.

[0007] Benzophenone derivatives are excellent ultraviolet photosensitizers that absorb not only 290-400nm ultraviolet light but also a portion of visible light. Due to their good compatibility with other materials, they are widely used in medicine, dyes, textiles, and other fields. Currently, there are few reports on the application of benzophenone derivative photosensitizers to down for antibacterial effects.

[0008] In summary, if a photosensitive antibacterial down can be provided, and non-natural photosensitizers can be used to finish the down so that it can obtain long-lasting antibacterial properties, and the antibacterial range is wide, and it can widely act on bacteria, fungi and other microorganisms, then the wearing performance of the down can be further improved. Summary of the Invention

[0009] In view of the above shortcomings of the prior art, the present invention provides a photosensitive antibacterial down and its preparation and application to solve the problems of poor antibacterial durability and narrow antibacterial range of down in the prior art.

[0010] To achieve the above-mentioned and related purposes, the present invention adopts the following technical solutions:

[0011] A method for preparing photosensitive antibacterial down, the method comprising the following steps:

[0012] (1) dissolving chitosan in an acetic acid solution to prepare a chitosan solution, adding the pretreated down to a glutaraldehyde aqueous solution, and then adding the chitosan solution to carry out a cross-linking reaction to obtain down cross-linked with chitosan;

[0013] (2) preparing a bimetallic coordinated supported benzophenone photosensitizer using 2,2'-hydroxy-4-methoxybenzophenone and any two of copper, nickel, and zinc metal salts as raw materials;

[0014] (3) activating the supported benzophenone photosensitizer in step (2);

[0015] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3) to carry out a condensation reaction to obtain photosensitive antibacterial down.

[0016] In one embodiment of the present application, the mass concentration of the chitosan solution in step (1) is 3-5%, and the volume ratio of the chitosan solution to the glutaraldehyde aqueous solution is (2-5):(20-40).

[0017] In one embodiment of the present application, the concentration of the glutaraldehyde aqueous solution in step (1) is 3-5%, the volume ratio of down to the glutaraldehyde aqueous solution is 1:(2-3), and the grafting reaction is carried out at 50-60° C. for 1.5-2 h.

[0018] In one embodiment of the present application, the metal salts of copper, nickel, and zinc in step (2) include zinc chloride, copper nitrate, and nickel chloride.

[0019] In one embodiment of the present application, the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone and any two of the metal salts of copper, nickel, and zinc in step (2) is one of the following: the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper metal salt, and zinc metal salt is (2-5): (1-2): (1-2);

[0020] In step (2), the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper metal salt, and nickel metal salt is (2-5): (1-3): (1-2);

[0021] In step (2), the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, nickel metal salt and zinc metal salt is (2-6): (2-3): (1-2.5).

[0022] In one embodiment of the present application, step (2) comprises: dissolving 2,2'-hydroxy-4-methoxybenzophenone in anhydrous ethanol, adding sodium hydroxide with a mass concentration of 2-4%, adding any two metal salts of copper, nickel, and zinc, reacting at 60-100°C for 1-3 hours, precipitating, filtering, washing, and drying to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0023] In one embodiment of the present application, step (3) comprises: dissolving the supported benzophenone photosensitizer in N,N-dimethylformamide, adding N-hydroxysulfosuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and stirring at 25-40° C. for 10-15 hours under nitrogen protection.

[0024] In one embodiment of the present application, the molar ratio of chitosan to the supported benzophenone photosensitizer is (1-2): (20-30).

[0025] The photosensitive antibacterial down prepared by the above-mentioned preparation method of the photosensitive antibacterial down.

[0026] Application of the photosensitive antibacterial down prepared by the above-mentioned preparation method of the photosensitive antibacterial down in textiles.

[0027] The beneficial technical effects of the present invention are:

[0028] 2,2'-Hydroxy-4-methoxybenzophenone has multiple coordinating atoms. Using 2,2'-hydroxy-4-methoxybenzophenone as a ligand and any two metal ions of copper, zinc, and nickel as central ions, a bimetallic-coordinated supported benzophenone photosensitizer is formed. Compared to benzophenone derivatives without metal coordination, the supported benzophenone photosensitizer prepared in this application is a hetero-binuclear chelate, which can enhance its ability to absorb ultraviolet light and has higher photostability. After the ligand and metal ion form a bond, the absorption peak of the benzophenone photosensitizer is enhanced and red-shifted, expanding the absorption range of light.

[0029] In addition, the loaded benzophenone photosensitizer prepared by complexing any two metal ions among copper, zinc and nickel is environmentally friendly, and the metal complexes show higher and broader antimicrobial activity than the ligands, thereby having better antibacterial properties, a wider antibacterial range, high reactivity and fast sterilization speed.

[0030] Since the photosensitizer is directly added to the down by impregnation, the loading amount is low, and the benzophenone photosensitizer, which is a pure organic compound, is volatile and has average photostability. As a result, the antibacterial down prepared by direct impregnation has poor durability and antibacterial effect. Therefore, the present application first cross-links chitosan to the down, and uses the chitosan to undergo a condensation reaction with the loaded benzophenone photosensitizer to generate a chitosan-based Schiff base metal complex, thereby increasing the loading amount of the loaded benzophenone photosensitizer on the down, thereby improving the antibacterial durability and broad-spectrum antibacterial properties of the down.

[0031] Chitosan also possesses excellent antibacterial properties. When condensed with supported benzophenone, it creates a synergistic effect, further enhancing the long-lasting antibacterial properties of down. Chitosan forms a permanent bond with down fibers through adsorption and linkage, imparting antibacterial and mildew-resistant properties to the down. Furthermore, the down has a high loft and a soft, full, and comfortable feel. Because chitosan is completely environmentally friendly and non-toxic to the human body, the resulting down meets environmental standards.

[0032] In summary, the photosensitive antibacterial down prepared in this application has long-lasting antibacterial properties, a wide antibacterial range, high safety, high antibacterial efficiency, and high photodynamic efficiency. The preparation method of this application has mild reaction conditions, low energy consumption, simple process, and is easy to industrialize. DETAILED DESCRIPTION

[0033] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the invention pertains. It should be understood that certain features of the present invention (described in the context of separate embodiments for clarity) may also be provided in combination in a single embodiment. On the contrary, a plurality of features of the present invention (described in the context of a single embodiment for brevity) may also be provided separately or in any suitable combination or in any other described embodiment of the present invention when appropriate. Certain features described in the context of various embodiments will not be considered as essential features of those embodiments unless the embodiment is inoperable without those elements. The present invention will be further described below by specific examples, but it should be noted that the specific process conditions and results described in the embodiments of the present invention are only used to illustrate the present invention and cannot limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and substance of the present invention should be included within the scope of protection of the present invention.

[0034] The present invention provides a method for preparing photosensitive antibacterial down, which comprises the following steps:

[0035] (1) dissolving chitosan in an acetic acid solution to prepare a chitosan solution, adding the pretreated down to a glutaraldehyde aqueous solution, and then adding the chitosan solution to carry out a cross-linking reaction to obtain down cross-linked with chitosan;

[0036] In this step, the preparation method of the pretreated down is as follows:

[0037] Wash down such as duck or goose down to remove surface dust or impurities, dry it, and set aside. Degrease the dried down by soaking it in a sodium hydroxide solution at a temperature of 40-60°C and a pH of 10-14 for 10-20 minutes. Drain the alkali solution, then soak the down in warm water at 40-60°C and then add a complex enzyme to the warm water for 10-15 minutes for a second degreasing step. The volume ratio of warm water to complex enzyme is 100:1, and the complex enzyme comprises protease and lipase at a volume ratio of 1:4. After enzyme washing, dehydrate and air dry the down to obtain pretreated down.

[0038] In this step, the concentration of the glutaraldehyde aqueous solution is 3-5%, the volume ratio of down to the glutaraldehyde aqueous solution is 1:(2-3), and the grafting reaction is carried out at 50-60°C for 1.5-2 hours. In this step, chitosan is dissolved in a 2-5% acetic acid solution to prepare a chitosan solution with a mass concentration of 3-5%, and the volume ratio of the chitosan solution to the glutaraldehyde aqueous solution is (2-5):(20-40).

[0039] (2) preparing a bimetallic coordinated supported benzophenone photosensitizer using 2,2'-hydroxy-4-methoxybenzophenone and any two of copper, nickel, and zinc metal salts as raw materials;

[0040] In this step, the metal salts of copper, nickel and zinc include zinc chloride, copper nitrate and nickel chloride.

[0041] In this step, the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone and any two of the metal salts of copper, nickel, and zinc is one of the following: the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper metal salt, and zinc metal salt is (2-5): (1-2): (1-2);

[0042] The molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper metal salt and nickel metal salt is (2-5): (1-3): (1-2);

[0043] The molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, nickel metal salt and zinc metal salt is (2-6):(2-3):(1-2.5).

[0044] In this step, 2,2'-hydroxy-4-methoxybenzophenone is dissolved in anhydrous ethanol, sodium hydroxide with a mass concentration of 2 to 4% is added, and any two metal salts of copper, nickel, and zinc are added. The reaction is kept at 60 to 100°C for 1 to 3 hours, precipitated, filtered under reduced pressure, washed with an ethanol-water solution with a volume ratio of 1:1, and dried to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0045] (3) activating the supported benzophenone photosensitizer in step (2);

[0046] In this step, the supported benzophenone photosensitizer is dissolved in N,N-dimethylformamide, and N-hydroxysulfosuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added. The mixture is stirred at 25-40° C. for 10-15 hours under nitrogen protection.

[0047] In this step, the molar ratio of the supported benzophenone photosensitizer, N-hydroxysulfosuccinimide, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is (1-2):(3-4):(3-4).

[0048] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3) to carry out a condensation reaction at a temperature of 30 to 50° C. for 6 to 10 hours to obtain photosensitive antibacterial down.

[0049] In some embodiments, the molar ratio of chitosan to supported photosensitizer is (1-2): (20-30).

[0050] The present invention provides photosensitive antibacterial down prepared by the above-mentioned method for preparing photosensitive antibacterial down.

[0051] The present invention provides application of the photosensitive antibacterial down prepared by the method for preparing the photosensitive antibacterial down in textiles.

[0052] The present invention is described in detail below by way of specific examples. It should also be understood that the following examples are only used to specifically illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, and those skilled in the art can make selections within a suitable range through the description herein, and are not to be limited to the specific numerical values ​​exemplified below.

[0053] Example 1

[0054] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 11 for 10 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 10 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated goose down.

[0055] 0.01 mol of chitosan was dissolved in a 3% acetic acid solution to prepare a chitosan solution with a mass concentration of 3%. The pretreated goose down was added to a 4% glutaraldehyde aqueous solution with a volume ratio of 1:2. The grafting reaction was carried out at 50°C for 1.5 hours. Then, the chitosan solution was added with a volume ratio of 2:25 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 60 minutes to obtain down cross-linked with chitosan.

[0056] (2) 0.1 mol of 2,2'-hydroxy-4-methoxybenzophenone was dissolved in 300 ml of anhydrous ethanol, and sodium hydroxide with a mass concentration of 2% was added, and 0.05 mol of copper nitrate and 0.05 mol of zinc chloride were added. The mixture was kept warm at 80°C for 1.5 h, precipitated, filtered under reduced pressure, washed with ethanol aqueous solution, and dried to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0057] (3) 0.1 mol of supported benzophenone photosensitizer was dissolved in N,N-dimethylformamide, and 0.3 mol of N-hydroxysulfosuccinimide and 0.3 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The mixture was stirred at 25°C for 10 h under nitrogen protection.

[0058] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3), and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0059] Example 2

[0060] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 12 for 12 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 12 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated goose down.

[0061] 0.01 mol of chitosan was dissolved in a 3% acetic acid solution to prepare a chitosan solution with a mass concentration of 4%. The pretreated goose down was added to a 5% glutaraldehyde aqueous solution with a volume ratio of 1:3. The grafting reaction was carried out at 50°C for 2 hours. Then, the chitosan solution was added with a volume ratio of 2:30 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 60 minutes to obtain down cross-linked with chitosan.

[0062] (2) 0.15 mol of 2,2'-hydroxy-4-methoxybenzophenone was dissolved in 300 ml of anhydrous ethanol, and sodium hydroxide with a mass concentration of 3% was added, and 0.08 mol of copper nitrate and 0.08 mol of nickel chloride were added. The mixture was kept at 80°C for 2 h, precipitated, filtered under reduced pressure, washed with ethanol aqueous solution, and dried to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0063] (3) 0.15 mol of supported benzophenone photosensitizer was dissolved in N,N-dimethylformamide, and 0.35 mol of N-hydroxysulfosuccinimide and 0.35 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The mixture was stirred at 25°C for 15 h under nitrogen protection.

[0064] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3), and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0065] Example 3

[0066] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 13 for 15 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 15 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated goose down.

[0067] 0.02 mol of chitosan was dissolved in 5% acetic acid solution to prepare a chitosan solution with a mass concentration of 5%. The pretreated goose down was added to a 5% glutaraldehyde aqueous solution with a volume ratio of 1:2. The grafting reaction was carried out at 50°C for 1.5 hours. Then the chitosan solution was added with a volume ratio of 3:40 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 70 minutes to obtain down cross-linked with chitosan.

[0068] (2) 0.3 mol of 2,2'-hydroxy-4-methoxybenzophenone was dissolved in 300 ml of anhydrous ethanol, and sodium hydroxide with a mass concentration of 2% was added, and 0.2 mol of nickel chloride and 0.1 mol of zinc chloride were added. The mixture was kept at 80°C for 1.5 h, precipitated, filtered under reduced pressure, washed with ethanol aqueous solution, and dried to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0069] (3) 0.1 mol of supported benzophenone photosensitizer was dissolved in N,N-dimethylformamide, and 0.15 mol of N-hydroxysulfosuccinimide and 0.15 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The mixture was stirred at 25°C for 10 h under nitrogen protection.

[0070] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3), and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0071] Example 4

[0072] (1) Wash the duck down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried duck down in a sodium hydroxide solution at 40°C and pH 10 for 10 minutes to degrease, and drain the alkali solution. Soak the duck down in 40°C warm water and then add a complex enzyme to the warm water for 10 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated duck down.

[0073] 0.01 mol of chitosan was dissolved in 3% acetic acid solution to prepare a chitosan solution with a mass concentration of 4%. The pretreated duck down was added to a 3% glutaraldehyde aqueous solution with a volume ratio of 1:2 between the goose down and the glutaraldehyde aqueous solution. The grafting reaction was carried out at 50°C for 2 hours. The chitosan solution was then added with a volume ratio of 2:40 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 60 minutes to obtain down cross-linked with chitosan.

[0074] (2) 0.1 mol of 2,2'-hydroxy-4-methoxybenzophenone was dissolved in 300 ml of anhydrous ethanol, and sodium hydroxide with a mass concentration of 5% was added, and 0.05 mol of copper nitrate and 0.05 mol of zinc chloride were added. The mixture was kept warm at 80°C for 1.5 h, precipitated, filtered under reduced pressure, washed with ethanol aqueous solution, and dried to obtain a bimetallic coordinated supported benzophenone photosensitizer.

[0075] (3) 0.1 mol of supported benzophenone photosensitizer was dissolved in N,N-dimethylformamide, and 0.18 mol of N-hydroxysulfosuccinimide and 0.15 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The mixture was stirred at 25°C for 12 h under nitrogen protection.

[0076] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3), and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0077] Comparative Example 1

[0078] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 11 for 10 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 10 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated goose down.

[0079] 0.01 mol of chitosan was dissolved in a 3% acetic acid solution to prepare a chitosan solution with a mass concentration of 3%. The pretreated goose down was added to a 4% glutaraldehyde aqueous solution with a volume ratio of 1:2. The grafting reaction was carried out at 50°C for 1.5 hours. Then, the chitosan solution was added with a volume ratio of 2:25 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 60 minutes to obtain down cross-linked with chitosan.

[0080] (2) Dissolve 0.1 mol of benzophenone photosensitizer in N,N-dimethylformamide, add 0.3 mol of N-hydroxysulfosuccinimide and 0.3 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and stir at 25°C for 10 h under nitrogen protection.

[0081] (3) The down cross-linked with chitosan in step (1) is immersed in an activated benzophenone photosensitizer, and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0082] Comparative Example 2

[0083] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 11 for 10 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 10 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated down.

[0084] (2) Dissolve 0.1 mol of benzophenone photosensitizer in N,N-dimethylformamide, add 0.3 mol of N-hydroxysulfosuccinimide and 0.3 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and stir at 25°C for 10 h under nitrogen protection.

[0085] (3) Immersing the down pretreated in step (1) in an activated benzophenone photosensitizer, performing a condensation reaction at 40° C. for 8 hours, and obtaining photosensitive antibacterial down.

[0086] Comparative Example 3

[0087] (1) Wash the goose down to remove dust or attached impurities on the surface, dry it and set it aside; soak the dried goose down in a sodium hydroxide solution at 40°C and pH 11 for 10 minutes to degrease, and drain the alkali solution. Soak the goose down in 40°C warm water and then add a complex enzyme to the warm water for 10 minutes to perform a second degreasing process. After enzyme washing, dehydrate and dry it to obtain pretreated goose down.

[0088] 0.01 mol of chitosan was dissolved in a 3% acetic acid solution to prepare a chitosan solution with a mass concentration of 3%. The pretreated goose down was added to a 4% glutaraldehyde aqueous solution with a volume ratio of 1:2. The grafting reaction was carried out at 50°C for 1.5 hours. Then, the chitosan solution was added with a volume ratio of 2:25 between the chitosan solution and the glutaraldehyde aqueous solution. The cross-linking reaction was carried out at 60°C for 60 minutes to obtain down cross-linked with chitosan.

[0089] (2) 0.1 mol of 2,2'-hydroxy-4-methoxybenzophenone was dissolved in 300 ml of anhydrous ethanol, and sodium hydroxide with a mass concentration of 1% was added, and 0.08 mol of copper nitrate was added. The reaction was kept at 80°C for 1 hour, precipitated, filtered under reduced pressure, washed with ethanol aqueous solution, and dried to obtain a single metal coordinated supported benzophenone photosensitizer.

[0090] (3) 0.1 mol of supported benzophenone photosensitizer was dissolved in N,N-dimethylformamide, and 0.3 mol of N-hydroxysulfosuccinimide and 0.3 mol of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. The mixture was stirred at 25°C for 10 h under nitrogen protection.

[0091] (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3), and a condensation reaction is carried out at 40° C. for 8 hours to obtain photosensitive antibacterial down.

[0092] Performance Testing

[0093] Antibacterial property: According to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", the antibacterial rates of the down prepared in Examples 1 to 4 and the down prepared in Comparative Examples 1 to 3 against Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231 were determined by the oscillation flask method. The results are shown in Table 1.

[0094] Fluffiness: The fluffiness of the down prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was tested in accordance with GB / T 17685-2016 "Down and Feathers". The specific testing method is as follows:

[0095] It should be noted that the down content of Examples 1 to 4 and Comparative Examples 1 to 3 of the present application is 95%, and no large down pieces are contained.

[0096] 30 g of each of the down prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was extracted as a test sample. Each test sample was placed in a loft tester with a diameter of 288 mm and a pressing plate weight of 94.3 g. The volume occupied by the down in the loft tester was tested. The test results are shown in Table 1.

[0097] Table 1 Performance test of down feathers in Examples and Comparative Examples

[0098]

[0099] (Note: The antibacterial rate against Staphylococcus aureus and Escherichia coli is ≥70%, and the antibacterial rate against Candida albicans is ≥60%. The sample has antibacterial effect;

[0100] Duck down with a down content of 95% and a fill power of ≥16.5cm is considered qualified; goose down with a down content of 95% and a fill power of ≥17.5cm is considered qualified)

[0101] As can be seen from Table 1, the antibacterial rates of the photosensitive antibacterial down of Examples 1 to 4 prepared by the preparation method of the present application against Staphylococcus aureus, Escherichia coli, and Candida albicans are all as high as 97%, which is much higher than the antibacterial rates of the down prepared in Comparative Examples 1 to 3. This shows that the down prepared by the present application has excellent antibacterial properties, broad antibacterial spectrum, and antibacterial stability. At the same time, the bulkiness of the photosensitive antibacterial down (goose down) of Examples 1 to 3 remains above 17.5 cm, and the bulkiness of the photosensitive antibacterial down (duck down) prepared in Example 4 is >16.5 cm, both of which are qualified products. This shows that the preparation method of the present application does not negatively affect the bulkiness of the down, and still has a high bulkiness, and thus the down prepared by the preparation method of the present application has good warmth retention.

[0102] Because the photosensitizer in Comparative Example 1 was not metal-modified, its photostabilization performance was poor, with inhibition rates against Staphylococcus aureus, Escherichia coli, and Candida albicans all below 80%, indicating poor antibacterial properties and stability. Furthermore, the down prepared in Comparative Example 1 exhibited a relatively low fill power, falling below the specified fill power of 17.5 cm, making the down unqualified and, to some extent, reducing its warmth.

[0103] The down prepared in Comparative Example 2 was not treated with chitosan, and the photosensitizer was not metal-modified. Consequently, the photosensitizer loading on the down was low. Consequently, the down prepared in Comparative Example 2 exhibited low antibacterial rates against Staphylococcus aureus, Escherichia coli, and Candida albicans, indicating poor antibacterial properties and stability. Furthermore, this preparation method significantly impacted the down's fluffiness, which fell far below the required standard of 17.5 cm. This resulted in poor warmth retention and a substandard down product.

[0104] Comparative Example 3, a chitosan condensation reaction with a monometallic benzophenone photosensitizer, yielded down with significantly higher antibacterial rates and improved fill power compared to the down from Comparative Examples 1-2. However, the down still fell below the required fill power standard of 17.5 cm, resulting in a product failure. Furthermore, the antibacterial rates and fill power were still inferior to those of the down treated with a bimetallic benzophenone photosensitizer from Examples 1-4.

[0105] In summary, the photosensitive antibacterial down prepared by the preparation method of the present application has excellent long-lasting antibacterial properties and a broad antibacterial range, showing excellent antibacterial effects against Gram-negative bacteria, Gram-positive bacteria, and fungi. Furthermore, the photosensitive antibacterial down prepared by the preparation method of the present application has high fluffiness and good warmth retention.

[0106] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A method for preparing photosensitive antibacterial down, characterized in that: The method comprises the following steps: (1) dissolving chitosan in an acetic acid solution to prepare a chitosan solution, adding the pretreated down to a glutaraldehyde aqueous solution, and then adding the chitosan solution to carry out a cross-linking reaction to obtain down cross-linked with chitosan; (2) preparing a bimetallic coordinated supported benzophenone photosensitizer using 2,2'-hydroxy-4-methoxybenzophenone and any two of copper, nickel, and zinc metal salts as raw materials; the copper, nickel, and zinc metal salts include zinc chloride, copper nitrate, and nickel chloride; (3) activating the supported benzophenone photosensitizer in step (2), comprising: dissolving the supported benzophenone photosensitizer in N,N-dimethylformamide, adding N-hydroxysulfosuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and stirring at 25-40° C. for 10-15 hours under nitrogen protection; (4) The down cross-linked with chitosan in step (1) is immersed in the loaded benzophenone photosensitizer activated in step (3) to carry out a condensation reaction to obtain photosensitive antibacterial down.

2. The method for preparing photosensitive antibacterial down according to claim 1, characterized in that: The mass concentration of the chitosan solution in step (1) is 3-5%, and the volume ratio of the chitosan solution to the glutaraldehyde aqueous solution is (2-5): (20-40).

3. The method for preparing photosensitive antibacterial down according to claim 1, characterized in that: In step (1), the concentration of the glutaraldehyde aqueous solution is 3-5%, the volume ratio of down to the glutaraldehyde aqueous solution is 1:(2-3), and the grafting reaction is carried out at 50-60° C. for 1.5-2 hours.

4. The method for preparing photosensitive antibacterial down according to claim 1, characterized in that: In step (2), the molar ratio of 2,2'-hydroxy-4-methoxybenzophenone and any two of the metal salts of copper, nickel and zinc is one of the following: The molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper nitrate, and zinc chloride is (2~5):(1~2):(1~2); The molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, copper nitrate, and nickel chloride is (2~5): (1~3): (1~2); The molar ratio of 2,2'-hydroxy-4-methoxybenzophenone, nickel chloride and zinc chloride is (2~6):(2~3):(1~2.5).

5. The method for preparing photosensitive antibacterial down according to claim 1, characterized in that: The step (2) comprises: dissolving 2,2'-hydroxy-4-methoxybenzophenone in anhydrous ethanol, adding sodium hydroxide with a mass concentration of 2-4%, adding any two metal salts of copper, nickel and zinc, reacting at 60-100°C for 1-3 hours, precipitating, filtering, washing and drying to obtain a bimetallic coordinated supported benzophenone photosensitizer.

6. The method for preparing photosensitive antibacterial down according to claim 1, characterized in that: The molar ratio of the chitosan to the supported benzophenone photosensitizer is (1-2): (20-30).

7. The photosensitive antibacterial down prepared by the method for preparing the photosensitive antibacterial down according to any one of claims 1 to 6.

8. Use of the photosensitive antibacterial down prepared by the method for preparing the photosensitive antibacterial down according to any one of claims 1 to 6 in textiles.

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