Antibacterial and antiviral material capable of releasing negative oxygen ions, preparation method and application on household board material

Abstract

This invention relates to the field of building materials, specifically to an antibacterial, antiviral, and negative ion-releasing material, its preparation method, and its application in furniture board materials. The preparation method includes: weighing an inorganic hydraulic cementitious material, a porous mineral carrier, a composite functional modifier, a dispersing and reinforcing agent, and water; reacting the porous mineral carrier with the composite functional modifier to prepare a supported composite functional modifier; then stirring the raw materials to obtain a slurry, which is then molded, cured, and demolded to obtain the final product. The composite functional modifier comprises a mixture of tourmaline-supported nano-silver and tourmaline-supported nano-copper. This invention, by constructing a two-stage loading system and combining it with the synergistic effect of the dispersing and reinforcing agent, ensures that the functional components are uniformly distributed within the material matrix, achieving integrated synergistic effects of antibacterial, antiviral, and negative ion-releasing functions. It also solves the problems of easy aggregation of functional components and poor durability of the surface functional layer.

Description

Technical Field

[0001] This invention relates to the field of building materials, specifically to an antibacterial and antiviral material that releases negative oxygen ions, its preparation method, and its application in furniture board materials. Background Technology

[0002] With the improvement of people's living standards and the increasing attention paid to healthy living environments, the environmental performance and functional characteristics of interior decoration materials have become an important development direction for the home furnishing industry. As an important component of interior space, home furnishing panels not only need to meet basic physical and mechanical properties and decorative effects, but are also increasingly endowed with multiple functions such as antibacterial, antiviral, and air purification. Negative oxygen ions, due to their positive effects on air purification and improving human function, have become one of the important indicators for measuring the health level of the indoor environment. Therefore, developing home furnishing panel materials that combine antibacterial, antiviral, and negative oxygen ion release functions has significant practical significance and application value.

[0003] Currently, several technical approaches have been proposed and applied for the functional modification of furniture panels. One common method involves introducing antibacterial agents (such as silver ions, copper ions, zinc ions, and their compounds) into the surface layer of the panel through surface coating or impregnation to achieve antibacterial and antiviral effects. However, this method often suffers from weak adhesion between the antibacterial layer and the substrate, poor durability, and easy wear and tear, and lacks targeted design for antiviral performance. Another technical approach involves adding inorganic negative oxygen ion powder (such as tourmaline and opal) to the panel matrix, relying on its spontaneous polarization effect to continuously release negative oxygen ions. However, these powders have poor dispersion in the matrix and are prone to agglomeration, leading to unstable negative oxygen ion release efficiency. Furthermore, excessive powder addition may weaken the mechanical strength of the panel. In addition, in existing technologies, antibacterial and antiviral functions and negative oxygen ion release functions are mostly introduced independently, lacking synergistic design and integrated management, making it difficult to achieve stable coexistence and long-term effectiveness of multiple functions while ensuring the overall performance of the panel.

[0004] Therefore, how to construct a material system that synergistically possesses antibacterial, antiviral, and negative oxygen ion-releasing functions, has a long-lasting effect, and is well-adaptable to various processes, while maintaining the good physical and mechanical properties of furniture boards, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to propose a material that is antibacterial, antiviral, and releases negative oxygen ions, thereby solving the problems in the prior art such as the difficulty in synergistic coexistence of antibacterial and antiviral functions and negative oxygen ion release functions, poor dispersibility and easy aggregation of functional components, and insufficient durability of surface functional layers.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions includes the following steps: Step 1: Weigh the raw materials; The raw materials, by weight, include: 100 parts of inorganic hydraulic cementitious material, 15-35 parts of porous mineral carrier, 5-15 parts of composite functional modifier, 0.6-3 parts of dispersing enhancer, and 25-45 parts of water. The composite functional modifier is loaded onto the porous mineral carrier to form a supported composite functional modifier. The composite functional modifier includes tourmaline-loaded inorganic nanoparticles; The tourmaline-loaded antibacterial inorganic nanoparticles are prepared by the following steps: Aminated tourmaline was reacted with an antibacterial inorganic salt solution to prepare tourmaline loaded with antibacterial ions; the tourmaline loaded with antibacterial ions was then reduced using a reducing agent to prepare tourmaline-loaded antibacterial inorganic nanoparticles. The tourmaline-loaded antibacterial inorganic nanoparticles include a mixture of tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles. Step 2: React the porous mineral carrier with the composite functional modifier to prepare the supported composite functional modifier; Step 3: Add the inorganic hydraulic cementitious material, the loaded composite functional modifier, the dispersing and reinforcing agent, and water into the mixer and stir to obtain the slurry; Step 4: Inject the slurry into the mold, vibrate to form, solidify, demold, and obtain the antibacterial, antiviral material that releases negative oxygen ions.

[0007] Preferably, in step one, the inorganic hydraulic cementitious material includes silicate cement; Porous mineral carriers include zeolites; Dispersion enhancers include mixtures of polycarboxylic acid superplasticizers and polyvinylpyrrolidone; The mass ratio of the polycarboxylic acid superplasticizer to the polyvinylpyrrolidone is 1:(0.2-1.5).

[0008] Preferably, in step one, when the tourmaline-loaded antibacterial inorganic nanoparticles are tourmaline-loaded silver nanoparticles, the preparation method of the tourmaline-loaded antibacterial inorganic nanoparticles specifically includes: Aminated tourmaline was dispersed in AgNO3 solution, the pH was adjusted to 7-8, and the mixture was stirred. After stirring, the mixture was centrifuged and washed to obtain tourmaline loaded with silver ions. Tourmaline loaded with silver ions was dispersed in deionized water, and a reducing agent solution was added dropwise. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain tourmaline-loaded silver nanoparticles.

[0009] Preferably, a pH value of 7-8 (neutral to weakly alkaline) is conducive to the amino chelation of silver ions.

[0010] Preferably, the mass ratio of aminated tourmaline to AgNO3 solution is 1:(40-60), and the stirring conditions are stirring at room temperature in the dark for 2-4 hours; the mass ratio of tourmaline loaded with silver ions to deionized water is 1:(20-40), the amount of reducing agent solution added is such that the molar ratio of reducing agent in the reducing agent solution to silver ions in the AgNO3 solution is (2-4):1, and the reaction conditions are stirring at room temperature for 30-60 minutes; The concentration of the AgNO3 solution is 0.01-0.05 mol / L; The concentration of the reducing agent solution is 0.01-0.05 mol / L; The reducing agent solution includes an aqueous solution of NaBH4.

[0011] Preferably, in step one, when the tourmaline-loaded antibacterial inorganic nanoparticles are tourmaline-loaded copper nanoparticles, the preparation method of the tourmaline-loaded antibacterial inorganic nanoparticles specifically includes: Aminated tourmaline was dispersed in Cu(NO3)2 solution, the pH was adjusted to 5-6, and the mixture was stirred. After stirring, the mixture was centrifuged, the precipitate was collected, washed, and copper-loaded tourmaline was obtained. Tourmaline loaded with copper ions was dispersed in deionized water, and a reducing agent solution was added dropwise. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain tourmaline-loaded copper nanoparticles.

[0012] Preferably, the pH value is set to 5-6 because copper ions are prone to hydrolysis and precipitation in a neutral or higher environment.

[0013] Preferably, the mass ratio of aminated tourmaline to Cu(NO3)2 solution is 1:(40-60), and the stirring conditions are stirring at room temperature for 2-4 hours; the mass ratio of copper-loaded tourmaline to deionized water is 1:(20-40), the amount of reducing agent solution added is such that the molar ratio of reducing agent in the reducing agent solution to copper ions in the Cu(NO3)2 solution is (2-3):1, and the reaction conditions are stirring at room temperature for 30-60 minutes under nitrogen protection; The concentration of the Cu(NO3)2 solution is 0.01-0.05 mol / L; The concentration of the reducing agent solution is 0.01-0.05 mol / L; The reducing agent solution includes an aqueous solution of NaBH4.

[0014] Preferably, the aminated tourmaline is prepared by the following steps: S1. Disperse the cleaned tourmaline powder in deionized water, adjust the pH value to 9-10, and perform activation treatment. After activation treatment, centrifuge, wash, and dry to obtain activated tourmaline powder. S2. Dissolve 3-aminopropyltriethoxysilane (silane coupling agent KH-550) in an aqueous ethanol solution, adjust the pH to 4-5, hydrolyze, add activated tourmaline powder, disperse by ultrasonication, react, centrifuge, wash, and dry to obtain aminated modified tourmaline.

[0015] Preferably, in step S1, the mass ratio of the cleaned tourmaline powder to deionized water is 1:(5-15), and the activation treatment is carried out by stirring and activating at 60-80℃ for 1-2 hours.

[0016] Preferably, in S2, the mass ratio of 3-aminopropyltriethoxysilane, aqueous ethanol solution, and activated tourmaline powder is 5:(80-120):(5-15), the hydrolysis conditions are stirring and hydrolysis at room temperature for 20-40 min, and the reaction conditions are stirring and reaction at 60-80℃ for 4-6 h.

[0017] Preferably, the ethanol aqueous solution is a 90wt% ethanol aqueous solution.

[0018] Preferably, the preparation method of the supported composite functional modifier in step two specifically includes: Tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles were mixed at a mass ratio of 1:(0.5-3) to obtain a composite functional modifier. The composite functional modifier was dispersed in an organic solvent and ultrasonically dispersed to obtain a composite functional modifier dispersion. The mass ratio of the composite functional modifier to the organic solvent is 1:(5-20); A porous mineral carrier was added to a dispersion of a composite functional modifier, with a mass ratio of (3-7):(1-3) for the porous mineral carrier to the composite functional modifier in the dispersion. After impregnation, the mixture was centrifuged, washed, and dried to obtain a supported composite functional modifier.

[0019] Preferably, the impregnation conditions are: impregnation at a vacuum of 0.05-0.09 MPa and a temperature of 50-70°C for 3-5 hours; The organic solvent includes anhydrous ethanol.

[0020] Preferably, in step three, the stirring conditions are: first stirring at a speed of 60-120 r / min for 3-5 min, and then stirring at a speed of 200-400 r / min for 8-12 min.

[0021] Preferably, in step four, the curing conditions are: curing for 7-28 days under conditions of relative humidity ≥90% and temperature 20±2℃.

[0022] The present invention also discloses an antibacterial, antiviral and negative oxygen ion releasing material, wherein the antibacterial, antiviral and negative oxygen ion releasing material is prepared by the preparation method of the antibacterial, antiviral and negative oxygen ion releasing material as described in any one of claims 1-8.

[0023] Application of a material that is antibacterial, antiviral, and releases negative oxygen ions, as described above, in furniture board materials.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: In this invention, nano-silver and nano-copper are respectively loaded onto the surface of aminated tourmaline to form two functional components: tourmaline-loaded nano-silver and tourmaline-loaded nano-copper, constructing a primary loading structure with tourmaline as the first-level carrier. Then, tourmaline-loaded nano-silver and tourmaline-loaded nano-copper are mixed in a specific ratio and loaded a second time onto the pores and surface of a porous mineral carrier using a vacuum impregnation process, constructing a secondary loading structure with the porous mineral carrier as the second-level carrier. This forms a two-level loading system of tourmaline—antibacterial metal nanoparticles—porous mineral carrier. The invention utilizes the inherent negative oxygen ion release properties of tourmaline and the nano-copper nanoparticles… The synergistic antibacterial and antiviral effects of silver nanoparticles and copper nanoparticles, along with the use of porous mineral carriers as a physical anchoring and protective matrix for functional components, avoid direct aggregation of nanoparticles in the inorganic hydraulic cementitious material matrix. Among these, the amination modification introduces amino functional groups into the surface of tourmaline, which on the one hand achieves efficient adsorption and uniform distribution of silver and copper ions through chelation, and on the other hand limits the growth size and aggregation degree of nanoparticles during the reduction process, ensuring the in-situ generation and stable loading of antibacterial metal nanoparticles on the tourmaline surface, providing a structural basis for the integrated synergistic effect of antibacterial and antiviral functions and negative oxygen ion release function. In this invention, a vacuum impregnation process is used to load composite functional modifiers into the pores of a porous mineral carrier. The porous structure of the mineral carrier provides physical confinement and protection for the functional components. On one hand, the antibacterial metal nanoparticles and tourmaline are encapsulated within the carrier's pores, preventing direct contact with the matrix and thus avoiding interfacial reactions or passivation during subsequent mixing and hydration hardening with inorganic hydraulic cementitious materials, ensuring the long-term stability of the functional components. On the other hand, the porous mineral carrier exists as an independent microdomain in the cured body, and its pore structure provides a continuous channel for the release of negative oxygen ions. Simultaneously, the antibacterial metal nanoparticles can slowly release trace amounts of metal ions in a humid environment, achieving long-lasting antibacterial and antiviral effects. The vacuum impregnation process ensures the uniform distribution and high loading rate of the functional components within the carrier pores, avoiding local enrichment or absence of functional components. In this invention, a dispersing and reinforcing agent composed of a polycarboxylate superplasticizer and polyvinylpyrrolidone is introduced. During the slurry mixing stage, the sedimentation and agglomeration of the loaded composite functional modifier in the multi-component slurry system are effectively suppressed through the synergistic effect of steric hindrance and electrostatic repulsion, ensuring that the functional components remain in a uniform suspension state in the slurry. During the hydration and hardening process, the polyvinylpyrrolidone molecular chains form hydrogen bonds with the hydrated calcium silicate gel, while the polycarboxylate superplasticizer regulates the hydration rate by adsorbing onto the surface of cement particles. The combined effect of these two factors ensures that the loaded composite functional modifier is uniformly distributed in the matrix phase of the hydrated and hardened body, rather than agglomerated at the interface or surface. This not only ensures the spatial uniformity of the functional components in the overall volume of the material and avoids the deterioration of mechanical properties caused by excessively high local concentrations, but also ensures that the antibacterial and antiviral functions and negative oxygen ion release functions of the material do not depend on the surface coating layer. Even after the surface layer of the material is worn, it can still maintain stable functionality, effectively solving the problem of insufficient durability of the surface functional layer in the prior art. Attached Figure Description

[0025] Figure 1 The image shown is a HAADF-STEM image of the supported composite functional modifier sample prepared in Example 6 of this invention. Figure 2 The graph shows the results of the antibacterial and antiviral properties of the materials that release negative oxygen ions and are prepared in Examples 4-6 and Comparative Examples 1-3 of this invention. Figure 3 The graph shows the results of the negative oxygen ion release performance measurement of the antibacterial and antiviral materials that release negative oxygen ions prepared in Examples 4-6 and Comparative Examples 1-3 of this invention. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0027] Example 1 This embodiment provides a method for preparing amino-modified tourmaline, including the following steps: S1. Tourmaline powder (particle size 17500 mesh) was added to anhydrous ethanol at a mass ratio of 1:20. After ultrasonic dispersion at 30 kHz for 20 min, the powder was centrifuged to remove surface organic impurities, and the cleaned tourmaline powder was obtained. The cleaned tourmaline powder was dispersed in deionized water, the pH was adjusted to 9.5, and the powder was activated by stirring at 70 ℃ for 1.5 h. After centrifugation at 8000 rpm for 10 min, the precipitate was washed three times with deionized water and dried to constant weight under vacuum at 50 ℃ to obtain activated tourmaline powder. S2. Dissolve 3-aminopropyltriethoxysilane in a 90wt% ethanol aqueous solution, adjust the pH to 4.5, stir and hydrolyze for 30 min at room temperature, add activated tourmaline powder, the mass ratio of 3-aminopropyltriethoxysilane, 90wt% ethanol aqueous solution and activated tourmaline powder is 5:100:10, ultrasonically disperse at 30kHz for 10 min, stir and react at 70℃ for 5 h, centrifuge at 8000rpm for 10 min, wash the centrifuged sediment three times each with anhydrous ethanol and deionized water, and dry to constant weight under vacuum at 50℃ to obtain aminated modified tourmaline.

[0028] Example 2 This embodiment provides a method for preparing tourmaline-supported silver nanoparticles, including the following steps: The aminated tourmaline obtained in Example 1 was dispersed in a 0.03 mol / L AgNO3 solution with a mass ratio of aminated tourmaline to AgNO3 solution of 1:50. The pH was adjusted to 7.5, and the mixture was stirred at room temperature in the dark for 3 hours. Then, it was centrifuged at 8000 rpm for 10 minutes. The centrifuged sediment was washed twice with deionized water to obtain tourmaline loaded with silver ions. Tourmaline loaded with silver ions was dispersed in deionized water at a mass ratio of 1:30. A 0.03 mol / L NaBH4 aqueous solution was added dropwise, with the amount of NaBH4 added being such that the molar ratio of NaBH4 in the NaBH4 aqueous solution to silver ions in the AgNO3 solution was 3:1. The mixture was stirred at room temperature for 45 min, and the solution color turned yellowish-brown. The mixture was centrifuged at 8000 rpm for 15 min. The precipitate was washed three times each with anhydrous ethanol and deionized water, and then dried under vacuum at 50 °C to constant weight to obtain tourmaline-loaded silver nanoparticles.

[0029] Example 3 This embodiment provides a method for preparing tourmaline-supported copper nanoparticles, including the following steps: The aminated tourmaline obtained in Example 1 was dispersed in a 0.03 mol / L Cu(NO3)2 solution, the pH was adjusted to 5.5, and the mixture was stirred at room temperature for 3 h. Then, it was centrifuged at 8000 rpm for 10 min. The centrifuged sediment was washed twice with deionized water to obtain tourmaline loaded with copper ions. Tourmaline loaded with copper ions was dispersed in deionized water at a mass ratio of 1:30. A 0.03 mol / L NaBH4 aqueous solution was added dropwise, with the amount of NaBH4 added being such that the molar ratio of NaBH4 in the NaBH4 aqueous solution to copper ions in the Cu(NO3)2 solution was 2.5:1. The reaction was carried out under nitrogen protection at room temperature with stirring for 45 min until the solution turned reddish-brown. The solution was centrifuged at 8000 rpm for 15 min. The precipitate was washed three times each with anhydrous ethanol and deionized water, and then dried at 50 °C under vacuum until constant weight to obtain tourmaline-loaded copper nanoparticles.

[0030] Example 4 This embodiment provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 15 parts of zeolite (325 mesh), 3.32 parts of tourmaline-loaded nano-silver prepared in Example 2, 1.68 parts of tourmaline-loaded nano-copper prepared in Example 3, 0.5 parts of polycarboxylate superplasticizer (HUAXUANPC-733, water reduction rate ≥25%), 0.1 parts of polyvinylpyrrolidone (PVP-K30), and 25 parts of water; In the above raw materials, the mass ratio of tourmaline-loaded nano-silver to tourmaline-loaded nano-copper is 1:0.5, the mass ratio of zeolite to composite functional modifier (the sum of tourmaline-loaded nano-silver and tourmaline-loaded nano-copper) is 3:1, and the mass ratio of polycarboxylate superplasticizer to polyvinylpyrrolidone is 1:0.2. Step 2: Mix tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles to obtain a composite functional modifier. Disperse the composite functional modifier in anhydrous ethanol at a mass ratio of 1:5 and ultrasonically disperse at 30kHz for 30 minutes to obtain a dispersion of the composite functional modifier. Zeolite was added to the dispersion of the composite functional modifier and impregnated under vacuum at 0.05 MPa and 50°C for 5 hours. After impregnation, the mixture was centrifuged at 8000 rpm for 10 minutes and then dried under vacuum at 50°C to constant weight to obtain the supported composite functional modifier. Step 3: Add silicate cement, load-bearing composite functional modifier, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 60 r / min for 5 min, then stir at 200 r / min for 12 min to obtain slurry. Step 4: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 7 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0031] Example 5 This embodiment provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 35 parts of zeolite (325 mesh), 3.75 parts of tourmaline-loaded nano-silver prepared in Example 2, 11.25 parts of tourmaline-loaded nano-copper prepared in Example 3, 1.2 parts of polycarboxylate superplasticizer (HUAXUANPC-733, water reduction rate ≥25%), 1.8 parts of polyvinylpyrrolidone (PVP-K30), and 45 parts of water; In the above raw materials, the mass ratio of tourmaline-loaded nano-silver to tourmaline-loaded nano-copper is 1:3, the mass ratio of zeolite to composite functional modifier (the sum of tourmaline-loaded nano-silver and tourmaline-loaded nano-copper) is 7:3, and the mass ratio of polycarboxylate superplasticizer to polyvinylpyrrolidone is 1:1.5. Step 2: Mix tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles to obtain a composite functional modifier. Disperse the composite functional modifier in anhydrous ethanol at a mass ratio of 1:20 and ultrasonically disperse at 30kHz for 30 minutes to obtain a composite functional modifier dispersion. Zeolite was added to the dispersion of the composite functional modifier and impregnated under vacuum at 0.09 MPa and 70°C for 3 hours. After impregnation, the mixture was centrifuged at 8000 rpm for 10 minutes and then dried under vacuum at 50°C to constant weight to obtain the supported composite functional modifier. Step 3: Add silicate cement, load-bearing composite functional modifier, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 120 r / min for 3 min, then stir at 400 r / min for 8 min to obtain slurry. Step 4: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 28 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0032] Example 6 This embodiment provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 25 parts of zeolite (325 mesh), 4 parts of tourmaline-loaded nano-silver prepared in Example 2, 6 parts of tourmaline-loaded nano-copper prepared in Example 3, 1 part of polycarboxylate superplasticizer (HUAXUAN PC-733, water reduction rate ≥25%), 0.8 parts of polyvinylpyrrolidone (PVP-K30), and 35 parts of water; In the above raw materials, the mass ratio of tourmaline-supported nano-silver to tourmaline-supported nano-copper is 1:1.5, the mass ratio of zeolite to composite functional modifier (the sum of tourmaline-supported nano-silver and tourmaline-supported nano-copper) is 5:2, and the mass ratio of polycarboxylate superplasticizer to polyvinylpyrrolidone is 1:0.8. Step 2: Mix tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles to obtain a composite functional modifier. Disperse the composite functional modifier in anhydrous ethanol at a mass ratio of 1:15 and ultrasonically disperse at 30 kHz for 30 min to obtain a dispersion of the composite functional modifier. Zeolite was added to the dispersion of the composite functional modifier and impregnated under vacuum at 0.07 MPa and 60°C for 4 hours. After impregnation, the mixture was centrifuged at 8000 rpm for 10 minutes and then dried under vacuum at 50°C to constant weight to obtain the supported composite functional modifier. Step 3: Add silicate cement, load-bearing composite functional modifier, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 90 r / min for 4 min, then stir at 300 r / min for 10 min to obtain slurry. Step 4: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 21 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0033] Comparative Example 1 This comparative example provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 15 parts of zeolite (325 mesh), 3.32 parts of tourmaline-loaded nano-silver prepared in Example 2, 1.68 parts of tourmaline-loaded nano-copper prepared in Example 3, 0.5 parts of polycarboxylate superplasticizer (HUAXUANPC-733, water reduction rate ≥25%), 0.1 parts of polyvinylpyrrolidone (PVP-K30), and 25 parts of water; In the above raw materials, the mass ratio of tourmaline-supported nano-silver to tourmaline-supported nano-copper is 1:0.5, and the mass ratio of polycarboxylate superplasticizer to polyvinylpyrrolidone is 1:0.2. Step 2: Add silicate cement, zeolite, tourmaline-loaded nano-silver, tourmaline-loaded nano-copper, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 60 r / min for 5 min, then stir at 200 r / min for 12 min to obtain slurry. Step 3: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 7 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0034] Comparative Example 2 This comparative example provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 15 parts of zeolite (325 mesh), 5 parts of tourmaline-supported nano-silver prepared in Example 2, 0.5 parts of polycarboxylate superplasticizer (HUAXUAN PC-733, water reduction rate ≥25%), 0.1 parts of polyvinylpyrrolidone (PVP-K30), and 25 parts of water; In the above raw materials, the mass ratio of zeolite to tourmaline-loaded nano-silver is 3:1, and the mass ratio of polycarboxylic acid superplasticizer to polyvinylpyrrolidone is 1:0.2. Step 2: Disperse tourmaline-loaded silver nanoparticles in anhydrous ethanol at a mass ratio of 1:5 and ultrasonically disperse at 30kHz for 30 minutes to obtain a tourmaline-loaded silver nanoparticle dispersion. Zeolite was added to tourmaline-supported nano-silver dispersion and impregnated under vacuum at 0.05 MPa and 50°C for 5 h. After impregnation, the mixture was centrifuged at 8000 rpm for 10 min and then dried under vacuum at 50°C to constant weight to obtain the supported functional modifier. Step 3: Add silicate cement, load-type functional modifier, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 60 r / min for 5 min, then stir at 200 r / min for 12 min to obtain slurry. Step 4: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 7 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0035] Comparative Example 3 This comparative example provides a method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, including the following steps: Step 1: Weigh the following raw materials according to the specified weight proportions: 100 parts of silicate cement (P·C32.5R), 15 parts of zeolite (325 mesh), 5 parts of tourmaline-loaded nano-copper prepared in Example 3, 0.5 parts of polycarboxylate superplasticizer (HUAXUAN PC-733, water reduction rate ≥25%), 0.1 parts of polyvinylpyrrolidone (PVP-K30), and 25 parts of water; In the above raw materials, the mass ratio of zeolite to tourmaline-loaded nano-copper is 3:1, and the mass ratio of polycarboxylate superplasticizer to polyvinylpyrrolidone is 1:0.2. Step 2: Disperse tourmaline-loaded copper nanoparticles in anhydrous ethanol at a mass ratio of 1:5 and ultrasonically disperse at 30kHz for 30 minutes to obtain a tourmaline-loaded copper nanoparticle dispersion. Zeolite was added to tourmaline-supported nano-copper dispersion and impregnated under vacuum at 0.05 MPa and 50°C for 5 h. After impregnation, the mixture was centrifuged at 8000 rpm for 10 min and then dried under vacuum at 50°C to constant weight to obtain the supported functional modifier. Step 3: Add silicate cement, load-type functional modifier, polycarboxylate superplasticizer, polyvinylpyrrolidone and water into a mixer. First, stir at 60 r / min for 5 min, then stir at 200 r / min for 12 min to obtain slurry. Step 4: Inject the slurry into the mold, vibrate to compact it, cover it with a moisturizing layer after molding, and cure it for 7 days under conditions of relative humidity ≥90% and temperature 20±2℃. Demold the material to obtain antibacterial, antiviral and negative oxygen ion release material.

[0036] Structural characterization and performance testing: (1) The supported composite functional modifier sample prepared in Example 6 was measured by high-angle annular dark-field imaging-scanning transmission electron microscopy (HAADF-STEM), and the measurement results are as follows: Figure 1As shown. By Figure 1 As can be seen from (a) and (b), Cu and Ag are both uniformly distributed as fine particles.

[0037] (2) Referring to standard GB / T21510-2008, the antibacterial and antiviral materials that release negative oxygen ions prepared in Examples 4-6 and Comparative Examples 1-3 were tested for antibacterial and antiviral properties using the film-coating method. The bacterial strains were Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538). Referring to standard ISO21702:2019, the antiviral properties of the antibacterial and antiviral materials that release negative oxygen ions prepared in Comparative Examples 1-3 were tested for antiviral properties using the virus titer assay. The virus strain was influenza A virus H1N1 (A / PR / 8 / 34). The results of the determination of the antibacterial rate of Escherichia coli, the antibacterial rate of Staphylococcus aureus, and the inactivation rate of H1N1 influenza virus are shown in Table 1. Table 1

[0038] As shown in Table 1, the antibacterial and antiviral material that releases negative oxygen ions prepared by this invention has excellent antibacterial and antiviral properties. The antibacterial rate against Escherichia coli is over 99%, the antibacterial rate against Staphylococcus aureus is over 98%, and the inactivation rate against H1N1 influenza virus is over 97%. Compared with Example 4: In Comparative Example 1, since the zeolite and tourmaline-loaded nano-silver and tourmaline-loaded nano-copper were not subjected to two-stage loading treatment, the functional components were directly dispersed in the cement matrix, resulting in severe agglomeration of the functional components in the matrix and a significant decrease in antibacterial and antiviral performance. In Comparative Example 2, only tourmaline-loaded nano-silver was used, and the antiviral performance was better than that of Comparative Example 3, which only used nano-copper, but lower than that of Example 4, which used both. This indicates that the synergistic use of nano-silver and nano-copper can achieve a better antiviral effect. In Comparative Example 3, only tourmaline-loaded nano-copper was used without adding tourmaline-loaded nano-silver, and both antibacterial and antiviral performance decreased. This indicates that the synergistic use of nano-silver and nano-copper can achieve a better antibacterial and antiviral effect, with nano-silver contributing more significantly to antibacterial performance and nano-copper playing an important supplementary role in antiviral performance.

[0039] (3) Referring to standard JC / T2110-2012, the negative oxygen ion release performance of the antibacterial and antiviral materials prepared in Examples 4-6 and Comparative Examples 1-3 was determined using the static closed chamber method and a negative oxygen ion tester. The volume of the test chamber was 1m³. 3 The measurement was conducted at a temperature of 25±2℃ and a relative humidity of 50±5% for 7 consecutive days. The results of the initial negative oxygen ion release, the negative oxygen ion release after 7 days, and the negative oxygen ion release attenuation rate are shown in Table 2. Table 2

[0040] As shown in Table 2, the antibacterial, antiviral, and negative ion-releasing material prepared by this invention exhibits excellent negative ion release performance, with an initial negative ion release amount reaching 1850 ions / cm³. 3 The highest number reached 2150 / cm. 3 The concentration of negative oxygen ions is much higher than that of ordinary silicate cement-based materials, and after continuous measurement for 7 days, the attenuation rate of negative oxygen ion release is less than 4%, demonstrating excellent release stability. Compared with Example 4: In Comparative Example 1, due to the lack of two-stage loading treatment, the functional components were unevenly dispersed in the cement matrix, and some functional components were encapsulated by cement hydration products, resulting in a lower initial release of negative oxygen ions than in Example 4. Moreover, the attenuation rate after 7 days was as high as 11.1%, which was much higher than in Example 4. This indicates that the porous structure of the porous mineral carrier in the two-stage loading system provides a continuous channel for the release of negative oxygen ions, ensuring the high efficiency and long-term stability of the release. In Comparative Example 2, only tourmaline was used to load nano-silver, and the negative oxygen ion release performance was basically the same as in Example 4. This indicates that the addition of nano-copper has little impact on the function of tourmaline in releasing negative oxygen ions, and the release of negative oxygen ions mainly depends on the spontaneous polarization effect of tourmaline itself. In Comparative Example 3, only tourmaline was used to load nano-copper, and the negative oxygen ion release performance was basically the same as in Example 4. This further verifies that the introduction of nano-silver and nano-copper has no significant negative impact on the negative oxygen ion release performance of tourmaline. The two-stage loading system successfully achieved the integrated synergy of antibacterial and antiviral functions and negative oxygen ion release functions.

[0041] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a material that is antibacterial, antiviral, and releases negative oxygen ions, characterized in that, Includes the following steps: Step 1: Weigh the raw materials; The raw materials, by weight, include: 100 parts of inorganic hydraulic cementitious material, 15-35 parts of porous mineral carrier, 5-15 parts of composite functional modifier, 0.6-3 parts of dispersing enhancer, and 25-45 parts of water. The composite functional modifier is loaded onto the porous mineral carrier to form a supported composite functional modifier. The composite functional modifier includes tourmaline-loaded inorganic nanoparticles; The tourmaline-loaded antibacterial inorganic nanoparticles are prepared by the following steps: Aminated tourmaline was reacted with an antibacterial inorganic salt solution to prepare tourmaline loaded with antibacterial ions; the tourmaline loaded with antibacterial ions was then reduced using a reducing agent to prepare tourmaline-loaded antibacterial inorganic nanoparticles. The tourmaline-loaded antibacterial inorganic nanoparticles include a mixture of tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles. Step 2: React the porous mineral carrier with the composite functional modifier to prepare the supported composite functional modifier; Step 3: Add the inorganic hydraulic cementitious material, the loaded composite functional modifier, the dispersing and reinforcing agent, and water into the mixer and stir to obtain the slurry; Step 4: Inject the slurry into the mold, vibrate to form, solidify, demold, and obtain the antibacterial, antiviral material that releases negative oxygen ions.

2. The method for preparing an antibacterial, antiviral material that releases negative oxygen ions according to claim 1, characterized in that, In step one, the inorganic hydraulic cementitious material includes silicate cement; Porous mineral carriers include zeolites; Dispersion enhancers include mixtures of polycarboxylic acid superplasticizers and polyvinylpyrrolidone; The mass ratio of the polycarboxylic acid superplasticizer to the polyvinylpyrrolidone is 1:(0.2-1.5).

3. The method for preparing a material with antibacterial and antiviral properties and that releases negative oxygen ions according to claim 1, characterized in that, In step one, when the tourmaline-loaded antibacterial inorganic nanoparticles are tourmaline-loaded silver nanoparticles, the preparation method of the tourmaline-loaded antibacterial inorganic nanoparticles specifically includes: Aminated tourmaline was dispersed in AgNO3 solution, the pH was adjusted to 7-8, and the mixture was stirred. After stirring, the mixture was centrifuged and washed to obtain tourmaline loaded with silver ions. The mass ratio of aminated tourmaline to AgNO3 solution was 1:(40-60), and the stirring conditions were 2-4 hours at room temperature in the dark. Tourmaline loaded with silver ions was dispersed in deionized water, a reducing agent solution was added dropwise, and the reaction was carried out. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain tourmaline-loaded silver nanoparticles. The mass ratio of tourmaline loaded with silver ions to deionized water is 1:(20-40), the amount of reducing agent solution added is such that the molar ratio of reducing agent to silver ions is (2-4):1, and the reaction conditions are stirring at room temperature for 30-60 min. The concentration of the AgNO3 solution is 0.01-0.05 mol / L; The concentration of the reducing agent solution is 0.01-0.05 mol / L; The reducing agent solution includes an aqueous solution of NaBH4.

4. The method for preparing a material with antibacterial and antiviral properties and that releases negative oxygen ions according to claim 3, characterized in that, In step one, when the tourmaline-loaded antibacterial inorganic nanoparticles are tourmaline-loaded copper nanoparticles, the preparation method of the tourmaline-loaded antibacterial inorganic nanoparticles specifically includes: Aminated tourmaline was dispersed in Cu(NO3)2 solution, the pH was adjusted to 5-6, and the mixture was stirred. After stirring, the mixture was centrifuged, the precipitate was collected, washed, and copper-loaded tourmaline was obtained. The mass ratio of aminated tourmaline to Cu(NO3)2 solution was 1:(40-60), and the stirring conditions were: stirring at room temperature in the dark for 2-4 hours. Tourmaline loaded with copper ions was dispersed in deionized water, a reducing agent solution was added dropwise, and the reaction was carried out. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain tourmaline-loaded copper nanoparticles. The mass ratio of tourmaline loaded with copper ions to deionized water is 1:(20-40), the amount of reducing agent solution added is such that the molar ratio of reducing agent to copper ions is (2-3):1, and the reaction conditions are: under nitrogen protection, stirring at room temperature for 30-60 min. The concentration of the Cu(NO3)2 solution is 0.01-0.05 mol / L; The concentration of the reducing agent solution is 0.01-0.05 mol / L; The reducing agent solution includes an aqueous solution of NaBH4.

5. The method for preparing an antibacterial, antiviral material that releases negative oxygen ions according to claim 1, characterized in that, The preparation method of the supported composite functional modifier in step two specifically includes: Tourmaline-loaded silver nanoparticles and tourmaline-loaded copper nanoparticles were mixed at a mass ratio of 1:(0.5-3) to obtain a composite functional modifier. The composite functional modifier was dispersed in an organic solvent and ultrasonically dispersed to obtain a composite functional modifier dispersion. The mass ratio of the composite functional modifier to the organic solvent is 1:(5-20); A porous mineral carrier was added to a dispersion of a composite functional modifier, with a mass ratio of (3-7):(1-3) for the porous mineral carrier to the composite functional modifier in the dispersion. After impregnation, the mixture was centrifuged, washed, and dried to obtain a supported composite functional modifier.

6. The method for preparing an antibacterial, antiviral material that releases negative oxygen ions according to claim 5, characterized in that, The impregnation conditions are: impregnation at a vacuum of 0.05-0.09 MPa and a temperature of 50-70°C for 3-5 hours; The organic solvent includes anhydrous ethanol.

7. The method for preparing a material with antibacterial and antiviral properties and that releases negative oxygen ions according to claim 1, characterized in that, In step three, the stirring conditions are as follows: first stir at a speed of 60-120 r / min for 3-5 minutes, and then stir at a speed of 200-400 r / min for 8-12 minutes.

8. The preparation method of an antibacterial, antiviral and negative oxygen ion releasing material according to claim 1, wherein in step four, the curing conditions are: curing for 7-28 days under conditions of relative humidity ≥90% and temperature 20±2℃.

9. A material that is antibacterial, antiviral, and releases negative oxygen ions, characterized in that, The material is prepared using the method described in any one of claims 1-8, which describes an antibacterial, antiviral material that releases negative oxygen ions.

10. The application of the antibacterial, antiviral, and negative ion-releasing material as described in claim 9 in home furnishing board materials.

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