Antibacterial ion controlled release fiber, air filtering material and preparation method thereof

Abstract

The invention discloses an antibacterial ion controlled release fiber, an air filtering material and a preparation method thereof, the antibacterial ion controlled release air filtering material comprises a fiber body, dopamine attached to the fiber body, an antibacterial agent deposited on the dopamine surface of the fiber body, and a controlled release layer attached to the surface of the antibacterial agent; the raw material of the controllable release layer is a substance which swells in a bacterial metabolism environment. The antibacterial filter material overcomes the defect that an antibacterial filter material disclosed in the prior art does not have a long-term effect, and has a sterilization function of controllable release of sterilization ions, the sterilization retention rate is greater than 99%, and the storage time is greater than 70 days.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of bacteriostatic air filtration materials, in particular to an antibacterial ion controlled release fiber, an air filtration material and a preparation method thereof. BACKGROUND

[0002] Air filtration materials with antibacterial function are important materials for realizing the purification of biological aerosols in closed spaces and preventing diseases caused by microorganisms. The antibacterial function of the filtration material is obtained by loading antibacterial materials (Ag, CuO, ZnO, TiO2, quaternary ammonium salt). The commonly used loading methods mainly include: dipping, aerosol deposition and mixed electrospinning. However, in the process of preparing the material by dipping method, the antibacterial substances are easy to block the pores of the filtration material and are not uniformly distributed, resulting in large resistance and high energy consumption of the prepared antibacterial air filtration material. The antibacterial filtration material prepared by using the filtration material to intercept the nano-silver particle aerosol has increased resistance after being loaded on the surface of the filtration material, and the nano-silver particles are easy to fall off from the surface of the fiber.

[0003] However, the antibacterial agents of the existing antibacterial filtration materials are uncontrollable during use, which leads to the non-long-acting nature of the bactericidal function of the filtration material. SUMMARY

[0004] Therefore, the technical problem to be solved by the present application is to overcome the defect that the antibacterial filtration material disclosed in the prior art does not have long-acting nature, so as to provide an antibacterial ion controlled release air filtration material and a preparation method thereof, which can effectively prolong the service life of the antibacterial material.

[0005] An antibacterial ion controlled release fiber comprises a fiber body, dopamine attached to the fiber body, an antibacterial agent deposited on the surface of the dopamine of the fiber body, and a controlled release layer attached to the surface of the antibacterial agent.

[0006] The raw materials of the controlled release layer include one or more of chitosan and PAA (polyacrylic acid).

[0007] The loading amount of the controlled release layer in the antibacterial ion controlled release fiber is 0.1 wt% or more, preferably 0.3% or more, and more preferably 0.3-50%. For example, the loading amount of the controlled release layer in the antibacterial ion controlled release fiber is 0.1 wt%, 0.3 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt% and the like.

[0008] The loading amount of the antibacterial agent in the antibacterial ion controlled release fiber is 0.2wt% or more, preferably 5wt%-30wt%. For example, the loading amount of the antibacterial agent in the antibacterial ion controlled release fiber is 0.2wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, etc.

[0009] The antibacterial agent includes one or more of Ag, CuO, ZnO, TiO2, and quaternary ammonium salt.

[0010] When the antibacterial agent includes one or more of Ag, CuO, ZnO, and TiO2, the loading amount of the antibacterial agent in the antibacterial ion controlled release fiber is 2wt% or more, preferably 5wt%-30wt%.

[0011] The fiber body includes one or more of cellulose fiber, Tencel fiber, glass fiber, PP fiber, PET fiber, and aramid fiber.

[0012] A preparation method of an antibacterial ion controlled release fiber, comprising:

[0013] Obtaining dopamine-mediated surface in-situ loading antibacterial agent fiber;

[0014] Preparation of the controlled release layer: mixing the dopamine-mediated surface in-situ loading antibacterial agent fiber with the controlled release layer solution, and obtaining the antibacterial ion controlled release fiber after cleaning.

[0015] The preparation process of the dopamine-mediated surface in-situ loading antibacterial agent fiber includes:

[0016] Attachment of dopamine: mixing the uniformly dispersed fiber body with the dopamine solution, and obtaining the surface deposited polydopamine fiber through stirring reaction;

[0017] Deposition of antibacterial agent: mixing the surface deposited polydopamine fiber with the antibacterial agent raw material solution, and obtaining the dopamine-mediated surface in-situ loading antibacterial agent fiber after reaction.

[0018] The concentration of the dopamine solution is 0.5g / L-4.0g / L;

[0019] And / or, the mass ratio of the fiber body to dopamine is (0.2-3.0):(0.5-4.0);

[0020] And / or, in the attachment step of the dopamine, the stirring reaction time is 12-24h.

[0021] When the antibacterial agent raw material solution includes a metal ion solution and a reducing agent, the concentration of the metal ions in the metal ion solution is 5-40g / L.

[0022] When the antibacterial agent raw material solution comprises a quaternary ammonium salt, the concentration of the antibacterial agent raw material solution is 0.2 wt% or more.

[0023] And / or, the metal ion solution comprises a silver ion solution, preferably a silver nitrate solution;

[0024] And / or, the reducing agent comprises one or more of sodium borohydride, glucose, sodium citrate or DMAB (dimethylaminobenzaldehyde);

[0025] And / or, the mass ratio of the surface polydopamine-deposited fiber to the antibacterial agent is 70:30-95:5.

[0026] The concentration of the controllable release layer solution is 0.1-10 g / L;

[0027] And / or, the mass ratio of the dopamine-mediated surface in-situ antibacterial agent-loaded fiber to the controllable release layer is (0.2-3):(0.01-0.1).

[0028] An antibacterial ion controllable release air filtration material is prepared by using fibers by a wet method; the fibers are the antibacterial ion controllable release fiber described above or the antibacterial ion controllable release fiber prepared by the preparation method described above.

[0029] Preferably, the wet method is a papermaking method.

[0030] The technical solution of the present application has the following advantages:

[0031] 1. The antibacterial ion controllable release fiber provided by the present application can improve the release rate of bactericidal ions in the antibacterial agent when the controllable release layer swells in an acidic or alkaline environment of bacterial metabolism, achieving a better bactericidal effect; and in an environment without bacteria, the molecular chains of the controllable release layer contract, inhibiting the release of antibacterial ions in the antibacterial agent, thereby effectively prolonging the effective life of the antibacterial material; that is, in a neutral environment without bacteria on the surface, the antibacterial ions (antibacterial agent) are released slowly, in an acidic or alkaline environment with bacteria, the antibacterial ions (antibacterial agent) are released quickly, having a bactericidal function of controllable release of bactericidal ions, a bactericidal retention rate > 99%, and a storage time > 70 days.

[0032] 2. In the method of the present application, the antibacterial filter material prepared by the polydopamine-mediated fiber is used to deposit antibacterial agents in situ, an antibacterial metal layer composed of silver, copper and other antibacterial agents is deposited on the surface in situ, and then a controllable release layer (chitosan, PAA, etc.) is modified on the surface of the antibacterial metal layer. The fiber with the in-situ deposited antibacterial agent and the controllable release layer is prepared into a high-efficiency air filter material by a wet method. The resistance of the filter material prepared by the method does not increase significantly. Compared with the antibacterial filter material prepared by the traditional immersion method, the filtration efficiency of the prepared filter material is increased by 10% to 30%, and the resistance is reduced by 10% to 30%. The killing rate of gram-positive bacteria and gram-negative bacteria is greater than 90%, and can even reach more than 99%.

[0033] 3. The antibacterial ion controllable release air filter material in the present application can be used for air purification in indoor (residential, commercial buildings, civil air defense engineering, closed cabin), effectively intercepting and killing biological aerosols. The antibacterial agent deposited on the surface of the fiber in situ makes the antibacterial agent uniformly loaded on the surface of the fiber body and avoids the problem of pore blockage between the fiber bodies. The prepared material has low resistance and low energy consumption. At the same time, the controllable release layer of the macromolecule on the surface of the antibacterial agent will respond to pH, so as to realize the effective release of the bactericidal ions in the antibacterial agent when there are bacteria on the surface of the air filter material. When there is no bacteria on the surface of the air filter material, the controllable release layer can inhibit the release of the bactericidal ions, effectively prolonging the duration of the killing rate of gram-positive bacteria and gram-negative bacteria being greater than 99%. DETAILED DESCRIPTION

[0034] The following examples are provided to better further understand the present application, and are not limited to the best mode of the present application, and do not limit the content and protection scope of the present application. Any product identical or similar to the present application obtained by the inspiration of the present application or the combination of the present application with other prior art features falls within the protection scope of the present application.

[0035] The specific experimental steps or conditions are not specified in the examples, and can be performed according to the conventional experimental steps described in the literature in the art or the operation or conditions. The reagents or instruments used are not specified by the manufacturer, and are conventional reagent products that can be obtained by purchase.

[0036] Example 1

[0037] An antibacterial ion controllable release fiber is prepared by the following method:

[0038] 1. Attachment of dopamine

[0039] A dopamine solution with a concentration of 2.0 g / L is configured, a certain amount of fiber body (cellulose fibers with a diameter of 15-30 μm and a length of 2-5 mm) is dispersed and then placed in the dopamine solution, the mass concentration of the fiber body after being added is 1.5 g / L, and the fiber body is stirred for 12 hours to obtain fibers with polydopamine deposited on the surface, and the mass ratio of the fiber body to dopamine is 1.5:2.

[0040] 2. Deposition of antibacterial agent

[0041] The fibers with polydopamine deposited on the surface are washed clean and then placed in a metal ion solution (i.e., a silver-ammonia solution; the silver-ammonia solution is obtained by adding 28-30% ammonia water dropwise in a silver nitrate solution with a concentration of 20 g / L until it is clear), and a fiber solution is obtained after the fibers are uniformly dispersed, a reducing agent (glucose) is added in the fiber solution after being uniformly dispersed, the content of the glucose in the metal ion solution after being added is 40 g / L, the fibers are taken out after the reaction is complete, washed clean with deionized water, and fibers with an antibacterial agent in situ loaded on the surface by dopamine mediation are obtained, and the mass ratio of the fibers with polydopamine deposited on the surface to the antibacterial agent is 100:8.

[0042] 3. Preparation of controllable release layer

[0043] 3 g of fibers with an antibacterial agent in situ loaded on the surface by dopamine mediation are soaked in 100 mL of a controllable release layer solution (a pH-sensitive polymer solution), the controllable release layer solution is a chitosan glacial acetic acid solution with a chitosan concentration of 0.1 g / L, the fibers are taken out after 120 min, washed clean with deionized water, and fibers with controllable release of antibacterial ions are obtained; wherein the glacial acetic acid solution is used as a solvent, and the material of the controllable release layer is chitosan. In this embodiment, the mass ratio of the fibers with an antibacterial agent in situ loaded on the surface by dopamine mediation to the controllable release layer is 3:0.01, that is, the loading amount of the controllable release layer in the fibers with controllable release of antibacterial ions is about 0.3 wt%.

[0044] An air filtration material with controllable release of antibacterial ions is prepared by the following method: the fibers with controllable release of antibacterial ions are used to prepare the air filtration material by a papermaking method.

[0045] The papermaking method is the steps of stock preparation, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the antibacterial ion controlled release fiber is prepared into fiber slurry, and the prepared fiber slurry is delivered to the forming net section through a pipeline. The fiber slurry forms a uniform wet air filter material on the high-speed running net belt in the forming net section. The wet air filter material is gradually dewatered through vacuum water suction tank, press roll and other equipment to form a semi-dry air filter material with certain strength. The semi-dry air filter material enters the drying section and is heated and dried through multiple groups of drying cylinders. Finally, the water content is reduced to about 5%. The dried air filter material is cut and slitted according to needs, and finally the finished product 1a is obtained.

[0046] Comparative Example 1

[0047] The difference from Example 1 is that the air filter material 1b is prepared by using the dopamine-mediated surface in-situ loaded antibacterial agent fiber in Example 1 to replace the antibacterial ion controlled release fiber, or the air filter material 1c is directly prepared by using the fiber body in Example 1 to replace the antibacterial ion controlled release fiber. The other processes of preparing the air filter material are the same as those in Example 1.

[0048] Example 2

[0049] An antibacterial ion controlled release fiber is prepared by the following method:

[0050] 1. Attachment of dopamine

[0051] A dopamine solution with a concentration of 0.5 g / L is configured. A certain amount of fiber body (using fibrillated Tencel fiber with an average diameter of 2 μm and a length of 1 mm) is dispersed and placed in the dopamine solution. The mass concentration of the fiber body after being added is 0.5 g / L. The stirring reaction is carried out for 24 hours to obtain the fiber with polydopamine deposited on the surface. The mass ratio of the fiber body to dopamine is 0.5:0.5.

[0052] 2. Deposition of antibacterial agent

[0053] The fiber with polydopamine deposited on the surface is washed clean and then dispersed uniformly in a metal ion solution (i.e. silver-ammonia solution; the silver-ammonia solution is obtained by adding 28-30% ammonia water dropwise into a 25 g / L silver nitrate solution until it is clear) to obtain a fiber solution. A reducing agent (glucose) is added into the uniformly dispersed fiber solution. The mass concentration of the glucose in the metal ion solution after being added is 50 g / L. After the reaction is completed, the fiber is taken out and washed clean with deionized water to obtain the dopamine-mediated surface in-situ loaded antibacterial agent fiber. The mass ratio of the fiber with polydopamine deposited on the surface to the antibacterial agent is 100:30.

[0054] 3. Preparation of controlled release layer

[0055] The dopamine-mediated surface in-situ loading of antibacterial agent fiber is immersed in 100 mL of a controllable release layer solution (a pH-sensitive polymer solution) which is a chitosan glacial acetic acid solution with a chitosan concentration of 1 g / L. After 240 min, the fiber is taken out and cleaned with deionized water to obtain an antibacterial ion controllable release fiber. In this embodiment, the mass ratio of the dopamine-mediated surface in-situ loading of antibacterial agent fiber to the controllable release layer is 2.5:0.1, i.e., the loading amount of the controllable release layer in the antibacterial ion controllable release fiber is about 4 wt%.

[0056] An antibacterial ion controllable release air filtration material is prepared by the following method: the antibacterial ion controllable release fiber is used to prepare the air filtration material by a papermaking method.

[0057] The papermaking method is the steps of pulp conditioning, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the antibacterial ion controllable release fiber is conditioned into fiber slurry, and the conditioned fiber slurry is delivered to the forming net section through a pipeline. The fiber slurry forms a uniform wet air filtration material on the high-speed running net belt in the forming net section. The wet air filtration material is gradually dewatered through vacuum water suction tank, pressing roller and other equipment to form a semi-dry air filtration material with certain strength. The semi-dry air filtration material enters the drying section and is dried by a plurality of drying cylinders. Finally, the water content is reduced to about 5%. The dried air filtration material is cut and slit according to needs, and finally the finished product 2a is obtained.

[0058] Comparative Example 2

[0059] The difference from Example 2 is that the dopamine-mediated surface in-situ loading of antibacterial agent fiber in Example 2 is used to replace the antibacterial ion controllable release fiber to prepare the air filtration material 2b, or the fiber body in Example 2 is used to replace the antibacterial ion controllable release fiber to directly prepare the air filtration material 2c. The other processes of preparing the air filtration material are the same as those in Example 2.

[0060] Example 3

[0061] An antibacterial ion controllable release fiber is prepared by the following method:

[0062] 1. Dopamine adhesion

[0063] A dopamine solution with a concentration of 4.0 g / L is configured, a certain amount of fiber body (glass fiber with an average diameter of 200 nm-1 μm and a length of 1-5 mm) is dispersed and then placed in the dopamine solution, the mass concentration of the fiber body after being added is 3.0 g / L, and the fiber body is stirred for 18 hours to obtain the fiber with polydopamine deposited on the surface, and the mass ratio of the fiber body to dopamine is 3:4.

[0064] 2. Deposition of antibacterial agent

[0065] The fiber with polydopamine deposited on the surface is washed clean and then placed in a metal ion solution (i.e. silver-ammonia solution; the silver-ammonia solution is obtained by adding 28-30% ammonia water into a silver nitrate solution with a concentration of 40 g / L until it is clear), and then uniformly dispersed to obtain a fiber solution, a reducing agent (glucose) is added into the uniformly dispersed fiber solution, the mass concentration of the glucose in the metal ion solution after being added is 80 g / L, and the fiber is taken out after the reaction is completed, washed clean with deionized water, and the fiber with the antibacterial agent in situ loaded on the surface is obtained, and the mass ratio of the fiber with polydopamine deposited on the surface to the antibacterial agent is 100:8.

[0066] 3. Preparation of controllable release layer

[0067] 2 g of the fiber with the antibacterial agent in situ loaded on the surface is soaked in 100 mL of a controllable release layer solution (pH-sensitive polymer solution) of chitosan glacial acetic acid solution with a concentration of 10 g / L, and the fiber is taken out after 180 min, washed clean with deionized water, and the fiber with controllable release of antibacterial ions is obtained; in this embodiment, the mass ratio of the fiber with the antibacterial agent in situ loaded on the surface to the controllable release layer is 2:1, that is, the loading amount of the controllable release layer in the fiber with controllable release of antibacterial ions is about 50 wt%.

[0068] An air filtration material with controllable release of antibacterial ions is prepared by the following method: the fiber with controllable release of antibacterial ions is used to prepare the air filtration material by a papermaking method.

[0069] The papermaking method is the steps of pulp conditioning, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the fiber with controllable release of antibacterial ions is conditioned into fiber slurry, the conditioned fiber slurry is delivered to the forming net section through a pipeline, the fiber slurry forms a uniform wet air filtration material on the high-speed running net belt, the wet air filtration material is gradually dewatered through a vacuum water suction tank, a press roll and other devices to form a semi-dry air filtration material with certain strength, the semi-dry air filtration material enters the drying section and is heated and dried through multiple groups of drying cylinders, and finally the water content is reduced to about 5%, the dried air filtration material is cut and slit according to needs, and finally the finished product 3a is obtained.

[0070] Comparative Example 3

[0071] The difference from Example 3 is that the air filtration material 3b is directly prepared by using the dopamine-mediated surface in-situ loaded antibacterial agent fiber in Example 3 to replace the antibacterial ion controlled release fiber, or the air filtration material 3c is directly prepared by using the fiber body in Example 3 to replace the antibacterial ion controlled release fiber, and the other processes of preparing the air filtration material are completely the same as those in Example 3.

[0072] Example 4

[0073] An antibacterial ion controlled release fiber is prepared by the following method:

[0074] 1. Attachment of dopamine

[0075] A dopamine solution with a concentration of 2 g / L is configured, and a certain amount of fiber body (PP fiber with a diameter of 17 μm and a length of 6 mm) is dispersed and placed in the dopamine solution. The mass concentration of the fiber body after being added is 1.0 g / L. The reaction is stirred for 18 hours to obtain a fiber with surface-deposited polydopamine. The mass ratio of the fiber body to dopamine is 1:2.

[0076] 2. Deposition of antibacterial agent

[0077] The fiber with surface-deposited polydopamine is washed clean and then dispersed uniformly in a metal ion solution (i.e. silver-ammonia solution; the silver-ammonia solution is obtained by adding 28-30% ammonia water dropwise in a silver nitrate solution with a concentration of 40 g / L until it is clear) to obtain a fiber solution. A reducing agent (sodium borohydride) is added to the fiber solution after uniform dispersion. The mass concentration of the sodium borohydride in the metal ion solution after being added is 50 g / L. After the reaction is completed, the fiber is taken out and washed clean with deionized water to obtain a dopamine-mediated surface in-situ loaded antibacterial agent fiber. The mass ratio of the fiber with surface-deposited polydopamine to the antibacterial agent is 100:25.

[0078] 3. Preparation of controlled release layer

[0079] 1 g of the dopamine-mediated surface in-situ loaded antibacterial agent fiber is soaked in 100 mL of a controlled release layer solution (pH-sensitive polymer solution) which is a chitosan glacial acetic acid solution with a chitosan concentration of 0.3 g / L. The fiber is taken out after 120 min and washed clean with deionized water to obtain an antibacterial ion controlled release fiber. In this example, the mass ratio of the dopamine-mediated surface in-situ loaded antibacterial agent fiber to the controlled release layer is 1:0.03, that is, the loading amount of the controlled release layer in the antibacterial ion controlled release fiber is about 3 wt%.

[0080] An air filter material with controllable release of antibacterial ions is prepared by the following method: the air filter material is prepared by papermaking method using the fiber with controllable release of antibacterial ions.

[0081] The papermaking method is the steps of pulp conditioning, flow delivery, molding, dehydration, drying and finishing in the conventional papermaking process. Specifically, the fiber with controllable release of antibacterial ions is conditioned into fiber slurry, and the conditioned fiber slurry is delivered to the forming net section through a pipeline. The fiber slurry forms a uniform wet air filter material on the high-speed running net belt in the forming net section. The wet air filter material is gradually dehydrated through vacuum water suction tank, press roller and other equipment to form semi-dry air filter material with certain strength. The semi-dry air filter material enters the drying section and is dried by heating through multiple groups of drying cylinders. The final water content is reduced to about 5%. The dried air filter material is cut and slit according to needs, and finally the finished product 4a is obtained.

[0082] Comparative Example 4

[0083] The difference from Example 4 is that the air filter material 4b is prepared by using the dopamine-mediated in-situ loaded antibacterial agent fiber in Example 4 instead of the fiber with controllable release of antibacterial ions, or the air filter material 4c is prepared by using the fiber body in Example 4 instead of the fiber with controllable release of antibacterial ions. The other processes of preparing the air filter material are the same as those in Example 4.

[0084] Example 5

[0085] A fiber with controllable release of antibacterial ions is prepared by the following method:

[0086] 1. Attachment of dopamine

[0087] A dopamine solution with a concentration of 1.0 g / L is configured, and a certain amount of fiber body (aramid fiber with a diameter of 12 μm and a length of 6 mm) is dispersed and placed in the dopamine solution. The mass concentration of the fiber body after addition is 2.0 g / L. The stirring reaction is carried out for 12 hours to obtain the fiber with polydopamine deposited on the surface. The mass ratio of the fiber body to dopamine is 1:2.

[0088] 2. Deposition of antibacterial agent

[0089] The surface polydopamine-deposited fiber is cleaned and then dispersed uniformly in a metal ion solution (i.e., a silver-ammonia solution; the silver-ammonia solution is obtained by adding 28-30% ammonia water dropwise into a 20 g / L silver nitrate solution until it is clear), to obtain a fiber solution, and then a reducing agent (sodium citrate) is added into the fiber solution, the mass concentration of the sodium citrate in the metal ion solution is 25 g / L after the addition, and after the reaction is completed, the fiber is taken out and cleaned with deionized water, to obtain a dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface, and the mass ratio of the surface polydopamine-deposited fiber to the antibacterial agent is 100:6.

[0090] 3. Preparation of the controllable release layer

[0091] The 1 g of dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface is soaked in 100 mL of a controllable release layer solution (a pH-sensitive polymer solution), the controllable release layer solution is a 2 g / L chitosan glacial acetic acid solution, and after 240 min, the fiber is taken out and cleaned with deionized water, to obtain an antibacterial ion controllable release fiber; in this embodiment, the mass ratio of the dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface to the controllable release layer is 1:0.2, that is, the loading amount of the controllable release layer in the antibacterial ion controllable release fiber is about 20 wt%.

[0092] An antibacterial ion controllable release air filtration material is prepared by the following method: the antibacterial ion controllable release fiber is used to prepare the air filtration material by a papermaking method.

[0093] The papermaking method is the steps of pulp conditioning, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the antibacterial ion controllable release fiber is conditioned into fiber slurry, the conditioned fiber slurry is delivered to the forming net part through a pipeline, the fiber slurry forms a uniform wet air filtration material on the high-speed running net belt in the forming net part, the wet air filtration material is gradually dewatered through a vacuum water suction tank, a press roll and other equipment, to form a semi-dry air filtration material with a certain strength, the semi-dry air filtration material enters the drying part and is heated and dried through multiple groups of drying cylinders, and finally the water content is reduced to about 5%, the dried air filtration material is cut and slit according to needs, and finally the finished product 5a is obtained.

[0094] Comparative Example 5

[0095] The difference from Example 5 is that the dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface in Example 5 is used to replace the antibacterial ion controllable release fiber to prepare the air filtration material 5b, or the fiber body in Example 5 is used to replace the antibacterial ion controllable release fiber to directly prepare the air filtration material 5c, and the other processes of preparing the air filtration material are the same as those in Example 5.

[0096] Example 6

[0097] An antibacterial ion controlled-release fiber is prepared by the following method:

[0098] 1. Dopamine attachment

[0099] A dopamine solution with a concentration of 2.0 g / L is prepared, and a certain amount of fiber bodies (cellulose fibers with a diameter of 15-30 μm and a length of 2-4 mm) are dispersed in the dopamine solution. The mass concentration of the fiber bodies after being added is 1.5 g / L. The mixture is stirred for 12 hours to obtain fibers with polydopamine deposited on the surface. The mass ratio of the fiber bodies to dopamine is 1.5:2.

[0100] 2. Deposition of antibacterial agent

[0101] The fibers with polydopamine deposited on the surface are washed and then dispersed in a metal ion solution (a mixed solution containing 50 mM copper chloride, 100 mM boric acid, and 50 mM EDTA, with the pH of the mixed solution adjusted to 7) to obtain a fiber solution. A reducing agent (DMAB solution) is added to the fiber solution, and the mass concentration of the DMAB in the metal ion solution is 100 mM (14.9 g / L). After the reaction is completed, the fibers are taken out and washed with deionized water to obtain dopamine-mediated fibers with an antibacterial agent in situ loaded on the surface. The mass ratio of the fibers with polydopamine deposited on the surface to the antibacterial agent is 100:15.

[0102] 3. Preparation of controlled-release layer

[0103] 1 g of dopamine-mediated fibers with an antibacterial agent in situ loaded on the surface is soaked in 100 mL of a controlled-release layer solution (a pH-sensitive polymer solution) with a concentration of 2 g / L. After 120 minutes, the fibers are taken out and washed with deionized water to obtain antibacterial ion controlled-release fibers. In this example, the mass ratio of the dopamine-mediated fibers with an antibacterial agent in situ loaded on the surface to the controlled-release layer is 1:0.2, i.e., the loading amount of the controlled-release layer in the antibacterial ion controlled-release fibers is about 20 wt%.

[0104] An antibacterial ion controlled-release air filtration material is prepared by the following method: the antibacterial ion controlled-release fibers are used to prepare the air filtration material by a papermaking method.

[0105] The papermaking method is the steps of stock preparation, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the antibacterial ion controlled release fiber is respectively prepared into fiber slurry, and the prepared fiber slurry is delivered to the forming net section through a pipeline. The fiber slurry forms a uniform wet air filter material on the high-speed running net belt in the forming net section. The wet air filter material is gradually dewatered through vacuum water suction box, press roll and other equipment to form semi-dry air filter material with certain strength. The semi-dry air filter material enters the drying section and is heated and dried through multiple groups of drying cylinders. Finally, the water content is reduced to about 5%. The dried air filter material is cut and slitted according to needs, and finally the finished product 6a is obtained.

[0106] Example 7

[0107] An antibacterial ion controlled release fiber is prepared by the following method:

[0108] 1. Dopamine attachment

[0109] A dopamine solution with a concentration of 2.0 g / L is prepared. A certain amount of fiber body (fibrillated nanocellulose fiber with a diameter of 200 nm-2 μm and a length of 1-3 mm) is dispersed and then put into the dopamine solution. The mass concentration of the fiber body after being added is 1.5 g / L. The mixture is stirred for 12 hours to obtain a fiber with polydopamine deposited on the surface. The mass ratio of the fiber body to dopamine is 1.5:2.

[0110] 2. Antibacterial agent deposition

[0111] The fiber with polydopamine deposited on the surface is washed clean and then dispersed in an antibacterial agent solution (2,3-epoxypropyltrimethylammonium chloride solution with a concentration of 0.1 g / L) to obtain a fiber solution. After the reaction is completed, the fiber is taken out and washed clean with deionized water to obtain a dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface. The mass ratio of the fiber with polydopamine deposited on the surface to the antibacterial agent 2,3-epoxypropyltrimethylammonium chloride is 400:1.

[0112] 3. Preparation of the controlled release layer

[0113] 5 g of the dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface is soaked in 100 mL of a controlled release layer solution (pH-sensitive polymer solution) which is a PAA solution with a concentration of 3 g / L. After 240 min, the fiber is taken out and washed clean with deionized water to obtain an antibacterial ion controlled release fiber. In this example, the mass ratio of the dopamine-mediated fiber with an antibacterial agent loaded in situ on the surface to the controlled release layer is 5:0.3, i.e., the loading amount of the controlled release layer in the antibacterial ion controlled release fiber is about 5.7 wt%.

[0114] An air filter material with controllable release of antibacterial ions is prepared by the following method: the fiber with controllable release of antibacterial ions is used to prepare the air filter material by papermaking method.

[0115] The papermaking method is the steps of stock preparation, flow delivery, molding, dewatering, drying and finishing in the conventional papermaking process. Specifically, the fiber with controllable release of antibacterial ions is prepared into fiber slurry, and the prepared fiber slurry is delivered to the forming net section through a pipeline. The fiber slurry forms a uniform wet air filter material on the high-speed running net belt. The wet air filter material is gradually dewatered through vacuum water suction tank, press roll and other equipment to form semi-dry air filter material with certain strength. The semi-dry air filter material enters the drying section and is dried by a plurality of drying cylinders. Finally, the water content is reduced to about 5%. The dried air filter material is cut and slit according to needs to obtain the finished product 7a.

[0116] Comparative Example 6

[0117] The difference from Example 1 is that the air filter material d is directly prepared by using the fiber with antibacterial agent loaded prepared by the conventional impregnation method in Example 1.

[0118] The preparation process of the fiber with antibacterial agent loaded prepared by the conventional impregnation method is as follows:

[0119] The fiber body is directly placed in a metal ion solution (the same antibacterial agent raw material solution in Example 1) to obtain a fiber solution. A reducing agent (40 g / L glucose solution) is added to the uniformly dispersed fiber solution. After the reaction is completed, the fiber is taken out and washed with deionized water to obtain the fiber with antibacterial agent loaded.

[0120] Experimental Example

[0121] The filtration efficiency (face flow rate 5.3 cm / s), resistance (face flow rate 5.3 cm / s) and storage time of the air filter materials of the examples and comparative examples with antibacterial efficiency greater than 99% are detected.

[0122] The detection process of the filtration efficiency (face flow rate 5.3 cm / s) and resistance (face flow rate 5.3 cm / s) is as follows:

[0123] According to the test method in standard GB 2626-2019 Respiratory Protection Self-suction Filter Type Particulate Matter Respirator, a single filter material efficiency detection table is used for testing.

[0124] The detection process of the antibacterial efficiency is as follows:

[0125] According to standard GB / T 20944.3-200 Evaluation of Antibacterial Performance of Textiles Part 3: Oscillation Method, the bactericidal efficiency of the antibacterial filter material is tested.

[0126] The detection process of the storage time with antibacterial retention rate greater than 99% is as follows:

[0127] The bactericidal efficiency of the filter material during the storage process is tested according to the antibacterial efficiency test method, and the days with antibacterial retention rate greater than 99% compared with the first detection are obtained.

[0128] The test results of the above examples and comparative examples are shown in Table 1.

[0129] Table 1

[0130]

[0131]

[0132] Obviously, the above examples are only examples for clearly illustrating but not limiting the embodiments. Other different forms of changes or variations can be made by those skilled in the art on the basis of the above description. All the embodiments do not need to be exhausted here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A fiber with controlled release of antibacterial ions, characterized in that: The invention comprises a fiber body, dopamine attached to the fiber body, an antibacterial agent deposited on the surface of the dopamine in the fiber body, and a controlled release layer attached to the surface of the antibacterial agent; The raw material of the controlled-release layer is a substance that swells in an environment of bacterial metabolism.

2. The fiber according to claim 1, characterized in that The raw materials of the controlled release layer include one or more of chitosan and PAA; and / or, the loading amount of the controlled-release layer in the antimicrobial ion controlled-release fiber is greater than 0.1 wt%; The loading amount of the antibacterial agent in the fiber capable of controlling the release of antibacterial ions is greater than 0.2 wt%.

3. The fiber according to claim 2, characterized in that The loading amount of the controlled-release layer in the antibacterial ion controlled-release fiber is 0.3%-50%; The loading amount of the antibacterial agent in the fiber capable of controlled release of antibacterial ions is 5 wt% to 30 wt%.

4. The fiber according to any one of claims 1 to 3, characterized in that The antibacterial agent includes one or more of Ag, CuO, ZnO, TiO2, and quaternary ammonium salts; The fiber body includes one or more of cellulose fiber, Tencel fiber, glass fiber, PP fiber, PET fiber, and aramid fiber.

5. A method for preparing a fiber with controlled release of antibacterial ions, characterized in that: include: Obtain dopamine-mediated in situ surface loading of antimicrobial agents on fibers; Preparation of the controlled-release layer: mixing the fibers with dopamine-mediated in-situ surface loading of antimicrobial agents with the controlled-release layer solution, and obtaining fibers with controlled-release of antimicrobial ions after cleaning; The controlled release layer solution includes substances that swell in the environment of bacterial metabolism.

6. The preparation method according to claim 5, characterized in that The preparation process of the dopamine-mediated surface in-situ antibacterial agent-loaded fiber includes: Dopamine attachment: Mix the evenly dispersed fiber body with the dopamine solution and stir to obtain fibers with polydopamine deposited on the surface; Deposition of antimicrobial agents: The fibers with polydopamine deposited on the surface are mixed with the antimicrobial agent raw material solution, and after the reaction, the fibers with dopamine-mediated surface in-situ loading of antimicrobial agents are obtained.

7. The preparation method according to claim 6, characterized in that The concentration of the dopamine solution is 0.5 g / L to 4.0 g / L; And / or, the mass ratio of the fiber body to dopamine is (0.2-3.0): (0.5-4.0); And / or, in the dopamine attachment step, the stirring reaction time is 12 to 24 hours; And / or, the antibacterial agent raw material solution includes a metal ion solution and a reducing agent.

8. The preparation method according to claim 7, characterized in that The concentration of the metal ion solution is 5 to 40 g / L; and / or, the metal ion solution comprises a silver ion solution, preferably a silver nitrate solution; And / or, the reducing agent includes one or more of sodium borohydride, glucose, sodium citrate or DMAB.

9. The preparation method according to any one of claims 5 to 8, characterized in that The concentration of the controlled release layer solution is 0.1 to 10 g / L; And / or, the mass ratio of the fiber with dopamine-mediated surface in situ loading of antibacterial agent to the controlled release layer is (0.2-3): (0.01-0.1).

10. A filter material with controlled release of antibacterial ions, prepared by wet process using fibers; characterized in that: The fiber is the antibacterial ion controllable release fiber according to any one of claims 1 to 4, or the antibacterial ion controllable release fiber prepared by the preparation method according to any one of claims 5 to 9.

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