Polymer antibacterial artificial leather and preparation method thereof

Abstract

The application discloses high-molecular antibacterial artificial leather and a preparation method thereof, and relates to the technical field of artificial leather preparation. In the application, zinc-loaded silica dioxide with grafted amino groups on the surface and quaternary ammonium polyether polyurethane containing epoxy groups are prepared, the two are mixed to prepare antibacterial protective slurry, and during solidification, the two are bonded through ring-opening reaction of the amino groups and the epoxy groups, a crosslinked network is formed, and an antibacterial protective layer with antibacterial property, softness and wear resistance is obtained; zinc ions have a significant inhibitory effect on bacteria such as gram-positive bacteria and gram-negative bacteria, and fungi such as Candida albicans, and quaternary ammonium salts have a significant inhibitory effect on influenza viruses; the two have a synergistic effect, the antibacterial range of the artificial leather is wider, the inhibitory effect on bacteria is stronger, and the antibacterial property of the artificial leather is further improved.

Description

Technical Field

[0001] This invention relates to the field of artificial leather preparation technology, specifically to a polymer antibacterial artificial leather and its preparation method. Background Technology

[0002] Artificial leather is made by foaming or coating PVC and PU onto non-woven or woven fabrics. It can be made with different strengths, glosses, and patterns according to different requirements. It has the advantages of being diverse, having high utilization rates, and being relatively inexpensive. Therefore, it is widely used in furniture, footwear, automotive interiors and other fields.

[0003] However, artificial leather has poor antibacterial properties and is prone to bacterial growth during use. For example, when artificial leather is used to make car interiors or sofas, different people will leave different bacteria on the surface after touching it. Over time, if it is not cleaned in time, bacteria will multiply in large numbers, which will not only produce odors but also easily spread infections.

[0004] Therefore, we propose a polymeric antibacterial artificial leather and its preparation method, which solves the above problems by preparing leather with antibacterial function. Summary of the Invention

[0005] The purpose of this invention is to provide a polymeric antibacterial artificial leather and its preparation method, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a polymer antibacterial artificial leather, comprising, from bottom to top, a non-woven fabric base layer, a foamed sheet, and an antibacterial protective layer; The foamed sheet is disposed on one side of the nonwoven base layer, and the antibacterial protective layer is disposed on the side of the foamed sheet away from the nonwoven base layer. The foamed sheet is obtained by calendering a foaming material, which includes the following components by weight: 90-110 parts polyvinyl chloride resin, 30-60 parts plasticizer, 4-6 parts calcium-zinc stabilizer, and 2-4 parts foaming agent.

[0007] Furthermore, the plasticizer is a mixture of trioctyl trimellitate and di(2-propylheptyl) adipate in a mass ratio of 1:(0.3~0.5); The foaming agent is one or a mixture of two of p-toluenesulfonamide and 4,4'-oxobisbenzenesulfonylhydrazine.

[0008] Furthermore, the antibacterial protective layer is obtained by coating an antibacterial protective slurry onto the surface of the foamed sheet away from the nonwoven base layer and then drying it. The antibacterial protective slurry comprises the following components by weight: 100 parts quaternized polyether polyurethane, 30-40 parts amino-terminated polydimethylsiloxane, 20-30 parts amino-modified filler, and 20-40 parts ethanol.

[0009] A method for preparing polymeric antibacterial artificial leather includes the following steps: Step 1: Mix polyvinyl chloride resin, plasticizer, and calcium-zinc stabilizer, stir evenly, and perform a first mixing. Then add foaming agent and perform a second mixing to obtain foamed material. Then calender to obtain foamed sheet. Step 2: Mix quaternized polyether polyurethane, ammonia-terminated polydimethylsiloxane, amino-modified filler, and ethanol, and stir evenly to obtain an antibacterial protective slurry. Step 3: Take the foamed sheet and bond it with the non-woven fabric. Coat the surface of the foamed sheet away from the non-woven fabric with an antibacterial protective slurry, cure it to obtain an antibacterial protective layer, and then heat-press and dry it in sequence to obtain polymer antibacterial artificial leather.

[0010] Furthermore, in step 1, the process conditions for one-time mixing are: temperature 125~135℃, time 10~15min; In step 1, the process conditions for secondary mixing are: temperature 125~165℃, time 30~50min.

[0011] Furthermore, in step 1, the foaming ratio of the foaming material is 0.6~0.8; In step 1, the rolling temperature is 165~175℃; In step 1, the thickness of the foamed sheet is 0.3~0.5mm.

[0012] Furthermore, in step 3, the curing process conditions are: temperature 60~70℃, time 1~2h; In step 3, the thickness of the antibacterial protective layer is 2~5μm.

[0013] Furthermore, in step 3, the hot pressing process conditions are: temperature 110~130℃, time 10~20s; In step 3, the drying process conditions are: 50~60℃, time 4~6h.

[0014] Furthermore, the quaternized polyether polyurethane is prepared by the following process: S1: Mix anhydrous polytetrahydrofuran diol with isophorone diisocyanate, heat and react. After the reaction is complete, cool down to 45~55℃, then add glycidol for end-capping reaction, then add dibutyltin dilaurate and continue the reaction for 1~2 hours to obtain epoxy-terminated polyether polyurethane prepolymer. S2: Mix epoxy-terminated polyether polyurethane prepolymer with N,N-dimethylformamide, stir until homogeneous, then add tetramethylhexanediamine, heat and stir to react, and obtain quaternized polyether polyurethane.

[0015] Furthermore, in S1, the mass ratio of anhydrous polytetrahydrofuran diol, isophorone diisocyanate, glycidol, and dibutyltin dilaurate is 1:(1.8~2.2):(2.0~2.4):(0.01~0.03).

[0016] Furthermore, in S1, the process conditions for the heating reaction are: temperature 75~85℃, time 2.0~2.5h; The process conditions for the end-capping reaction are: temperature 65~75℃, time 1.8~2.2h.

[0017] Furthermore, in S2, the mass ratio of epoxy-terminated polyether polyurethane prepolymer, N,N-dimethylformamide, and tetramethylhexanediamine is 15:(40~50):(4~6).

[0018] Furthermore, the tetramethylhexanediamine is added in solution form; The solution was prepared by mixing tetramethylhexanediamine and acetic acid in a molar ratio of 2:(2~3).

[0019] Furthermore, in S2, the process conditions for heating and stirring the reaction are: temperature 80~90℃, time 2~3h, and rotation speed 150~200r / min.

[0020] In the above technical solution, firstly, anhydrous polytetrahydrofuran diol reacts with isophorone diisocyanate, controlling the excess of isophorone diisocyanate to obtain isocyanate-terminated polyether polyurethane. Then, glycidol reacts with isocyanate groups to obtain an epoxy-terminated polyether polyurethane prepolymer. Next, tetramethylhexanediamine is mixed with acetic acid to prepare tetramethylhexanediamine acetate, converting the highly reactive free tertiary amine into a less reactive quaternary ammonium salt. Compared to directly adding tetramethylhexanediamine, the reaction process is more controllable. To avoid uneven reaction, the quaternary ammonium salt gradually decomposes after heating, slowly releasing free tertiary amines, which then undergo ring-opening addition with epoxy groups to obtain quaternized polyether polyurethane. During the reaction, the excess of epoxy-terminated polyether polyurethane prepolymer is controlled so that epoxy groups remain in the quaternized polyether polyurethane. Finally, by mixing the quaternized polyether polyurethane with amino-terminated polydimethylsiloxane, amino-modified fillers, etc., an antibacterial protective slurry is obtained. After coating, the epoxy groups react with the amino groups during the curing process to produce crosslinking, thus obtaining an antibacterial protective layer. In the above process, the antibacterial protective layer, foamed sheet, and non-woven fabric are pressed together by hot pressing, which softens or slightly melts the antibacterial protective layer. This allows it to penetrate at the interface of the materials, and the molecular chains become entangled, forming a tightly interwoven structure. This prevents the interlayer from cracking and peeling during use, further extending its service life. The amino-modified filler, quaternized polyether polyurethane, and ammonia-terminated polydimethylsiloxane are chemically bonded, making the bond stronger and less prone to migration. The molecular chains are mainly composed of polyether segments, giving the product softness and hydrolysis resistance. The added ammonia-terminated polydimethylsiloxane can also further improve the soft feel and wear resistance, making it suitable for sofas, automotive interiors, and other fields.

[0021] Furthermore, the preparation process of the amino-modified filler is as follows: Step A: Mix hollow silica and zinc salt solution, disperse by ultrasonication, evacuate to -0.1~-0.3MPa, let stand for 20~40min, restore to normal pressure, repeat evacuation, standing, and restoration to normal pressure 3~5 times, centrifuge and dry to obtain zinc-loaded silica; Step B: Disperse zinc-loaded silica in a triethanolamine aqueous solution, add an amino coupling agent, stir to disperse, adjust the pH to 8-9, and continue stirring for 3-5 hours to obtain an amino-modified filler.

[0022] Furthermore, in step A, the ratio of hollow silica to zinc salt solution is 10g:(180~220)mL; The zinc salt solution is one or a mixture of two of zinc sulfate and zinc nitrate. The zinc salt solution has a mass fraction of 20-50%.

[0023] Furthermore, in step A, the ultrasonic dispersion process conditions are: frequency 30~50kHz, time 20~40min; The centrifugation process conditions are: rotation speed 3000~5000 r / min, time 4~8 min; In step A, the drying process conditions are: temperature 40~50℃, time 4~8h.

[0024] Furthermore, in step B, the mass ratio of zinc-loaded silica, triethanolamine aqueous solution, and amino coupling agent is 1:(15~20):(0.3~0.5).

[0025] Furthermore, the mass fraction of the triethanolamine aqueous solution is 3-5%; The amino coupling agent is added in the form of an aqueous solution, with a mass fraction of 30-40%. The amino coupling agent is one or a mixture of γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

[0026] In the above technical solution, zinc ions are loaded onto silica through coordination, and then an amino coupling agent is used for surface modification to introduce amino groups, so that the amino groups can undergo a ring-opening reaction with the epoxy groups involved in the quaternized polyether polyurethane. Hollow silica, as a filler, can disperse stress and improve the tensile strength and abrasion resistance of the leather. Zinc ions have a significant inhibitory effect on bacteria such as Gram-positive bacteria and Gram-negative bacteria, as well as fungi such as Candida albicans. Quaternary ammonium salts have an inhibitory effect on influenza viruses. The synergistic effect of the two can make the antibacterial range of artificial leather wider and the inhibitory power against pathogens stronger, further improving its antibacterial properties.

[0027] Compared with the prior art, the beneficial effects of the present invention are: 1. In this application, amino-modified filler, quaternized polyether polyurethane and ammonia-terminated polydimethylsiloxane are chemically bonded to make the bond stronger and less prone to migration. The molecular chain is mainly composed of polyether segments, which makes the product soft and hydrolysis resistant. The added ammonia-terminated polydimethylsiloxane can also further improve the soft feel and wear resistance, making it suitable for sofas, automotive interiors and other fields.

[0028] 2. In this application, hollow silica, as a filler, can disperse stress and improve the tensile strength and abrasion resistance of the leather. Zinc ions have a significant inhibitory effect on bacteria such as Gram-positive bacteria and Gram-negative bacteria, as well as fungi such as Candida albicans. Quaternary ammonium salts have an inhibitory effect on influenza viruses. The synergistic effect of the two can make the antibacterial range of artificial leather wider and the inhibitory power against pathogens stronger, further improving the antibacterial properties.

[0029] 3. In this application, the antibacterial protective layer, foamed sheet and non-woven fabric are pressed together by hot pressing, so that the antibacterial protective layer softens or melts slightly, and penetrates at the interface of the materials. The molecular chains are entangled to form a tightly interwoven structure, which prevents the interlayer from cracking and peeling during use, and further improves its service life. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0031] In the following specific implementation, Non-woven fabric base layer, item number yy230422, sourced from Dongguan Youyu Industrial Investment Co., Ltd. Polyvinyl chloride resin, grade E68CT, is sourced from Dongguan Caihua Plastics Technology Co., Ltd. Ammonia-terminated polydimethylsiloxane, catalog number xyh001, is sourced from Hubei Xinyuhong Biomedical Technology Co., Ltd. Hollow silica, product number JK-04-018-150, pore size 4~6nm, particle size 150nm, sourced from Nanjing Jike Biotechnology Co., Ltd. Aminated hollow silica, with a pore size of 5-8 nm and a particle size of 100-120 nm, is sourced from Shaanxi Xingbei Aike Biotechnology Co., Ltd. The foaming agent is p-toluenesulfonamide; The amino coupling agent is γ-aminopropyltriethoxysilane; The zinc salt solution is a zinc sulfate solution; Waterborne polyurethane, model PU-106, is from Shanghai Bolino New Materials Technology Co., Ltd.

[0032] Example 1: A method for preparing a polymeric antibacterial artificial leather, comprising the following steps: (1) Preparation of amino-modified fillers: Hollow silica and zinc salt solution were mixed, ultrasonically dispersed, and evacuated to -0.1 MPa. The mixture was allowed to stand for 40 min, then returned to normal pressure. This process of evacuation, standing, and returning to normal pressure was repeated 5 times. The mixture was then centrifuged to obtain zinc-loaded silica. Step B: The zinc-loaded silica was dispersed in a triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane was added. The mixture was stirred and dispersed, and the pH was adjusted to 9. Stirring was continued for 5 h to obtain an amino-modified filler. In Step A, the ratio of hollow silica to zinc sulfate solution was 10 g: 220 mL; the mass fraction of the zinc sulfate solution was... 50%; In step A, the ultrasonic dispersion process conditions are: frequency 50kHz, time 40min; the centrifugation process conditions are: speed 5000r / min, time 8min; In step A, the drying process conditions are: temperature 50℃, time 8h; In step B, the mass ratio of zinc-loaded silica, triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane is 1:20:0.5; the mass fraction of the triethanolamine aqueous solution is 5%; γ-aminopropyltriethoxysilane is added in the form of an aqueous solution with a mass fraction of 40%. (2) Preparation of quaternized polyether polyurethane: S1: Anhydrous polytetrahydrofuran diol and isophorone diisocyanate were mixed and heated to react. After the reaction was completed, the temperature was lowered to 55°C, and then glycidol was added for end-capping reaction. Then dibutyltin dilaurate was added, and the reaction was continued for 2 hours to obtain epoxy-terminated polyether polyurethane prepolymer. S2: The epoxy-terminated polyether polyurethane prepolymer was mixed with N,N-dimethylformamide and stirred evenly. Then tetramethylhexanediamine solution was added, and the mixture was heated and stirred to react to obtain quaternized polyether polyurethane. In S1, the mass ratio of anhydrous polytetrahydrofuran diol, isophorone diisocyanate, glycidol, and dibutyltin dilaurate was 1:2.2:2.4:0.03. In S1, the heating reaction conditions were: temperature 75°C, time 2.0 h; the end-capping reaction conditions were: temperature 65°C, time 1.8 h. In S2, the epoxy-terminated polyether polyurethane prepolymer, N, The mass ratio of N-dimethylformamide to tetramethylhexanediamine solution is 15:50:6; the tetramethylhexanediamine solution is prepared by mixing tetramethylhexanediamine and acetic acid in a molar ratio of 2:2; in S2, the process conditions for heating and stirring reaction are: temperature 90℃, time 3h, rotation speed 200r / min; (3) Preparation of polymer antibacterial artificial leather: Step 1: Mix 110 parts of polyvinyl chloride resin, 60 parts of plasticizer, and 6 parts of calcium-zinc stabilizer, stir evenly, and perform a first mixing. Then add 4 parts of foaming agent and perform a second mixing to obtain a foamed material. Calender the mixture to obtain a foamed sheet. Step 2: Mix 100 parts of quaternized polyether polyurethane, 40 parts of amino-terminated polydimethylsiloxane, 30 parts of amino-modified filler, and 40 parts of ethanol, stir evenly, to obtain an antibacterial protective slurry. Step 3: Lay the foamed sheet onto a non-woven fabric. Coat the surface of the foamed sheet away from the non-woven fabric with the antibacterial protective slurry, cure, and obtain an antibacterial protective layer. Then, hot-press and dry sequentially to obtain a polymeric antibacterial artificial leather. In Step 1, the plasticizer is trioctyl trimellitate and... A mixture of di(2-propylheptane) adipate at a mass ratio of 1:0.5; in step 1, the process conditions for the first mixing are: temperature 135℃, time 15min; in step 1, the process conditions for the second mixing are: temperature 165℃, time 50min; in step 1, the foaming ratio of the foaming material is 0.8; in step 1, the calendering temperature is 175℃; in step 1, the thickness of the foamed sheet is 0.5mm; in step 3, the curing process conditions are: temperature 70℃, time 2h; in step 3, the thickness of the antibacterial protective layer is 5μm; in step 3, the hot pressing process conditions are: temperature 130℃, time 20s; in step 3, the drying process conditions are: 60℃, time 6h.

[0033] Example 2: A method for preparing a polymeric antibacterial artificial leather, comprising the following steps: (1) Preparation of amino-modified fillers: Hollow silica and zinc salt solution were mixed, ultrasonically dispersed, and evacuated to -0.2 MPa. The mixture was allowed to stand for 30 minutes, then returned to normal pressure. This process of evacuation, standing, and returning to normal pressure was repeated four times. The mixture was then centrifuged to obtain zinc-loaded silica. Step B: The zinc-loaded silica was dispersed in a triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane was added. The mixture was stirred and dispersed, and the pH was adjusted to 9. Stirring was continued for 4 hours to obtain an amino-modified filler. In Step A, the ratio of hollow silica to zinc sulfate solution was 10 g: 200 mL; the mass fraction of the zinc sulfate solution was... 35%; In step A, the ultrasonic dispersion process conditions are: frequency 40kHz, time 30min; the centrifugation process conditions are: speed 4000r / min, time 6min; In step A, the drying process conditions are: temperature 45℃, time 6h; In step B, the mass ratio of zinc-loaded silica, triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane is 1:18:0.4; the mass fraction of the triethanolamine aqueous solution is 4%; γ-aminopropyltriethoxysilane is added in the form of an aqueous solution with a mass fraction of 35%; (2) Preparation of quaternized polyether polyurethane: S1: Anhydrous polytetrahydrofuran diol and isophorone diisocyanate were mixed and heated to react. After the reaction was completed, the temperature was lowered to 50°C, and then glycidol was added for end-capping reaction. Dibutyltin dilaurate was then added, and the reaction was continued for 1.5 h to obtain epoxy-terminated polyether polyurethane prepolymer. S2: The epoxy-terminated polyether polyurethane prepolymer was mixed with N,N-dimethylformamide and stirred evenly. Tetramethylhexanediamine solution was then added, and the mixture was heated and stirred to react to obtain quaternized polyether polyurethane. In S1, the mass ratio of anhydrous polytetrahydrofuran diol, isophorone diisocyanate, glycidol, and dibutyltin dilaurate was 1:2.0:2.2:0.02. In S1, the heating reaction conditions were: temperature 80°C, time 2.3 h; the end-capping reaction conditions were: temperature 70°C, time 2.0 h. In S2, the epoxy-terminated polyether polyurethane prepolymer, N, The mass ratio of N-dimethylformamide to tetramethylhexanediamine solution is 15:45:5; the tetramethylhexanediamine solution is prepared by mixing tetramethylhexanediamine and acetic acid in a molar ratio of 2:2.5; in S2, the process conditions for heating and stirring reaction are: temperature 85℃, time 2.5h, rotation speed 180r / min; (3) Preparation of polymer antibacterial artificial leather: Step 1: Mix 100 parts polyvinyl chloride resin, 45 parts plasticizer, and 5 parts calcium-zinc stabilizer, stir evenly, and perform a first mixing. Then add 3 parts foaming agent and perform a second mixing to obtain a foamed material. Calender the mixture to obtain a foamed sheet. Step 2: Mix 100 parts quaternized polyether polyurethane, 35 parts amino-terminated polydimethylsiloxane, 25 parts amino-modified filler, and 30 parts ethanol, stir evenly, to obtain an antibacterial protective slurry. Step 3: Lay the foamed sheet onto a non-woven fabric. Coat the surface of the foamed sheet away from the non-woven fabric with the antibacterial protective slurry, cure, and obtain an antibacterial protective layer. Then, hot-press and dry sequentially to obtain a polymeric antibacterial artificial leather. In Step 1, the plasticizer is trioctyl trimellitate and hexyl... The mixture of di(2-propylheptane) diacid by mass ratio 1:0.4; the process conditions for the first mixing in step 1 are: temperature 130℃, time 13min; the process conditions for the second mixing in step 1 are: temperature 145℃, time 40min; the foaming ratio of the foaming material in step 1 is 0.7; the calendering temperature in step 1 is 170℃; the thickness of the foamed sheet in step 1 is 0.4mm; the curing process conditions in step 3 are: temperature 65℃, time 1.5h; the thickness of the antibacterial protective layer in step 3 is 3μm; the hot pressing process conditions in step 3 are: temperature 120℃, time 15s; the drying process conditions in step 3 are: 55℃, time 5h.

[0034] Example 3: A method for preparing a polymeric antibacterial artificial leather, comprising the following steps: (1) Preparation of amino-modified fillers: Hollow silica and zinc salt solution were mixed, ultrasonically dispersed, and evacuated to -0.3 MPa. The mixture was allowed to stand for 20 minutes, then returned to normal pressure. This process of evacuation, standing, and returning to normal pressure was repeated three times. The mixture was then centrifuged to obtain zinc-loaded silica. Step B: The zinc-loaded silica was dispersed in a triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane was added. The mixture was stirred and dispersed, and the pH was adjusted to 8. Stirring was continued for 3 hours to obtain an amino-modified filler. In Step A, the ratio of hollow silica to zinc sulfate solution was 10 g: 180 mL; the mass fraction of the zinc sulfate solution was... 20%; In step A, the ultrasonic dispersion process conditions are: frequency 30kHz, time 20min; the centrifugation process conditions are: speed 3000r / min, time 4min; In step A, the drying process conditions are: temperature 40℃, time 4h; In step B, the mass ratio of zinc-loaded silica, triethanolamine aqueous solution, and γ-aminopropyltriethoxysilane is 1:15:0.3; the mass fraction of the triethanolamine aqueous solution is 3%; γ-aminopropyltriethoxysilane is added in the form of an aqueous solution with a mass fraction of 30%. (2) Preparation of quaternized polyether polyurethane: S1: Anhydrous polytetrahydrofuran diol and isophorone diisocyanate were mixed and heated to react. After the reaction was completed, the temperature was lowered to 45°C, and then glycidol was added for end-capping reaction. Then dibutyltin dilaurate was added, and the reaction was continued for 1 hour to obtain epoxy-terminated polyether polyurethane prepolymer. S2: The epoxy-terminated polyether polyurethane prepolymer was mixed with N,N-dimethylformamide and stirred evenly. Then tetramethylhexanediamine solution was added, and the mixture was heated and stirred to react to obtain quaternized polyether polyurethane. In S1, the mass ratio of anhydrous polytetrahydrofuran diol, isophorone diisocyanate, glycidol, and dibutyltin dilaurate was 1:1.8:2.0:0.01. In S1, the heating reaction conditions were: temperature 75°C, time 2.0 h; the end-capping reaction conditions were: temperature 65°C, time 1.8 h. In S2, the epoxy-terminated polyether polyurethane prepolymer, N, The mass ratio of N-dimethylformamide to tetramethylhexanediamine solution is 15:40:4; the tetramethylhexanediamine solution is prepared by mixing tetramethylhexanediamine and acetic acid in a molar ratio of 2:3; in S2, the process conditions for heating and stirring reaction are: temperature 80℃, time 2h, rotation speed 150r / min; (3) Preparation of polymer antibacterial artificial leather: Step 1: Mix 90 parts polyvinyl chloride resin, 30 parts plasticizer, and 4 parts calcium-zinc stabilizer, stir evenly, and perform a first mixing. Then add 2 parts foaming agent and perform a second mixing to obtain a foamed material. Calender the mixture to obtain a foamed sheet. Step 2: Mix 100 parts quaternized polyether polyurethane, 30 parts amino-terminated polydimethylsiloxane, 20 parts amino-modified filler, and 20 parts ethanol, stir evenly, to obtain an antibacterial protective slurry. Step 3: Lay the foamed sheet onto a non-woven fabric. Coat the surface of the foamed sheet away from the non-woven fabric with the antibacterial protective slurry, cure, and obtain an antibacterial protective layer. Then, hot-press and dry sequentially to obtain a polymeric antibacterial artificial leather. In Step 1, the plasticizer is trioctyl trimellitate and hexyl... A mixture of di(2-propylheptane) diacid at a mass ratio of 1:0.3; in step 1, the process conditions for the first mixing are: temperature 125℃, time 10min; in step 1, the process conditions for the second mixing are: temperature 125℃, time 30min; in step 1, the foaming ratio of the foaming material is 0.6; in step 1, the calendering temperature is 165℃; in step 1, the thickness of the foamed sheet is 0.3mm; in step 3, the curing process conditions are: temperature 60℃, time 1h; in step 3, the thickness of the antibacterial protective layer is 2μm; in step 3, the hot pressing process conditions are: temperature 110℃, time 10s; in step 3, the drying process conditions are: 50℃, time 4h.

[0035] Comparative Example 1: Compared with Example 1, the amino-modified filler was replaced with aminated hollow silica, and the other conditions remained the same as in Example 1.

[0036] Comparative Example 2: Compared with Example 1, the epoxy-terminated polyether polyurethane prepolymer was not quaternized. Instead, the epoxy-terminated polyether polyurethane prepolymer was directly mixed with ammonia-terminated polydimethylsiloxane, amino-modified filler, and ethanol to prepare an antibacterial protective slurry. All other conditions remained unchanged and were the same as in Example 1.

[0037] Comparative Example 3: Compared with Example 1, the mass ratio of epoxy-terminated polyether polyurethane prepolymer, N,N-dimethylformamide, and tetramethylhexanediamine solution was 15:50:25. The epoxy groups in the system were basically consumed, and the resulting quaternized polyether polyurethane did not contain epoxy groups. The other conditions remained unchanged and were the same as in Example 1.

[0038] Comparative Example 4: Compared with Example 1, the quaternized polyether polyurethane was replaced with waterborne polyurethane, and the other conditions remained the same as in Example 1.

[0039] Comparative Example 5: Compared with Example 1, the amino-modified filler was replaced with aminated hollow silica, and the quaternized polyether polyurethane was replaced with waterborne polyurethane. All other conditions remained the same as in Example 1.

[0040] Experiment: The polymeric antibacterial artificial leather obtained in the examples and comparative examples was tested for various properties; Antibacterial test: The polymeric antibacterial artificial leather obtained in the examples and comparative examples was cut into 5×5cm samples as test samples, and a blank sample was set up; the test samples were immersed in a solution of 3×10 5 The bacterial culture medium containing CFU / mL was shaken at 150 r / min for 18 h, then incubated at 37 ℃ for 24 h. The number of colonies before and after shaking was measured, and the antibacterial properties were calculated. Antibacterial rate = (AB) / A × 100%; A represents the number of colonies after shaking the blank sample; B represents the number of colonies after the test sample is shaken; Antiviral test: The antiviral performance of the polymer antibacterial artificial leather prepared in the examples and comparative examples was tested according to GB / T 43823-2024.

[0041] Based on the data in Table 1, the following conclusions can be drawn: Compared with Example 1, the inhibition rate of influenza A virus in Comparative Examples 2 and 4 decreased. This is because zinc ions have a poor inhibitory effect on influenza virus. Therefore, the antibacterial performance decreased when quaternary ammonium salt was not added. The overall antibacterial rate in Comparative Example 3 did not change significantly, indicating that the simultaneous addition of zinc ions and quaternary ammonium salts improved the antibacterial rate. The overall antibacterial rate of Comparative Example 5 decreased significantly, with no antibacterial effect, indicating that the modified filler and quaternized polyether polyurethane prepared in this application can promote the comprehensive improvement of the antibacterial rate of the prepared polymer antibacterial artificial leather. Abrasion resistance test: The tensile strength and abrasion resistance of the polymer antibacterial artificial leather obtained in the examples and comparative examples were tested in accordance with GB / T 8949-2008.

[0042] Based on the data in Table 2, the following conclusions can be drawn: Compared with Example 1, the tensile strength of Comparative Examples 1 and 2 did not change significantly; the tensile strength and abrasion resistance of the artificial leathers made in Comparative Examples 3, 4 and 5 deteriorated significantly because they did not contain epoxy groups and could not form a cross-linked structure with amino groups, thus resulting in a decrease in mechanical properties. In summary, the process conditions and material formulations specified in this application can promote the overall improvement of the mechanical properties of the produced polymer antibacterial artificial leather.

[0043] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A polymeric antibacterial artificial leather, characterized in that: From bottom to top, it includes a non-woven base layer, a foamed sheet, and an antibacterial protective layer; The antibacterial protective layer is obtained by coating and curing an antibacterial protective slurry. The antibacterial protective slurry comprises the following components by weight: 100 parts quaternized polyether polyurethane, 30-40 parts amino-terminated polydimethylsiloxane, 20-30 parts amino-modified filler, and 20-40 parts ethanol. The quaternized polyether polyurethane is prepared by the following process: S1: Mix anhydrous polytetrahydrofuran diol with isophorone diisocyanate, heat and react. After the reaction is complete, cool down to 45~55℃, then add glycidol for end-capping reaction, then add dibutyltin dilaurate and continue the reaction for 1~2 hours to obtain epoxy-terminated polyether polyurethane prepolymer. S2: Mix epoxy-terminated polyether polyurethane prepolymer with N,N-dimethylformamide, stir until uniform, then add tetramethylhexanediamine, heat and stir to react, and obtain quaternized polyether polyurethane. The tetramethylhexanediamine was added in solution form; The solution was prepared by mixing tetramethylhexanediamine and acetic acid in a molar ratio of 2:(2~3); In S2, the mass ratio of epoxy-terminated polyether polyurethane prepolymer, N,N-dimethylformamide, and tetramethylhexanediamine is 15:(40~50):(4~6).

2. The polymeric antibacterial artificial leather according to claim 1, characterized in that: In S1, the mass ratio of anhydrous polytetrahydrofuran diol, isophorone diisocyanate, glycidol, and dibutyltin dilaurate is 1:(1.8~2.2):(2.0~2.4):(0.01~0.03).

3. The method for preparing a polymeric antibacterial artificial leather according to claim 1, characterized in that: Includes the following steps: Step 1: Mix polyvinyl chloride resin, plasticizer, and calcium-zinc stabilizer, stir evenly, and perform a first mixing. Then add foaming agent and perform a second mixing to obtain foamed material. Then calender to obtain foamed sheet. Step 2: Mix quaternized polyether polyurethane, ammonia-terminated polydimethylsiloxane, amino-modified filler, and ethanol, and stir evenly to obtain an antibacterial protective slurry. Step 3: Take the foamed sheet and bond it with the non-woven fabric. Coat the surface of the foamed sheet away from the non-woven fabric with an antibacterial protective slurry, cure it to obtain an antibacterial protective layer, and then heat-press and dry it in sequence to obtain polymer antibacterial artificial leather.

4. The method for preparing a polymeric antibacterial artificial leather according to claim 3, characterized in that: The preparation process of the amino-modified filler is as follows: Step A: Mix hollow silica and zinc salt solution, disperse by ultrasonication, evacuate to -0.1~-0.3MPa, let stand for 20~40min, restore to normal pressure, repeat evacuation, standing, and restoration to normal pressure 3~5 times, centrifuge and dry to obtain zinc-loaded silica; Step B: Disperse zinc-loaded silica in a triethanolamine aqueous solution, add an amino coupling agent, stir to disperse, adjust the pH to 8-9, and continue stirring for 3-5 hours to obtain an amino-modified filler.

5. The method for preparing a polymeric antibacterial artificial leather according to claim 4, characterized in that: In step A, the ratio of hollow silica to zinc salt solution is 10g: (180~220)mL; The zinc salt solution has a mass fraction of 20-50%.

6. The method for preparing a polymeric antibacterial artificial leather according to claim 4, characterized in that: In step B, the mass ratio of zinc-loaded silica, triethanolamine aqueous solution, and amino coupling agent is 1:(15~20):(0.3~0.5). The mass fraction of the triethanolamine aqueous solution is 3-5%; The amino coupling agent is added in the form of an aqueous solution with a mass fraction of 30-40%.

7. The method for preparing a polymeric antibacterial artificial leather according to claim 3, characterized in that: In step 3, the hot pressing process conditions are: temperature 110~130℃, time 10~20s.

8. The method for preparing a polymeric antibacterial artificial leather according to claim 3, characterized in that: The foaming material comprises the following components by weight: 90-110 parts polyvinyl chloride resin, 30-60 parts plasticizer, 4-6 parts calcium-zinc stabilizer, and 2-4 parts foaming agent.

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