A composite antibacterial and antiviral plate and a preparation method of a composite antibacterial and antiviral agent

Abstract

The application relates to the technical field of antibacterial and antiviral plates, and discloses a composite antibacterial and antiviral plate and a composite antibacterial and antiviral agent, which comprises two substrates, the two substrates are provided with balance layers at one end, adhesive agents are arranged between the two substrates and the two balance layers, and antibacterial and antiviral impregnated decorative papers are arranged between the two balance layers. The composite antibacterial and antiviral plate is formed by combining various antibacterial and antiviral technologies to form a novel composite antibacterial and antiviral agent. Compared with general antibacterial or antiviral plates, the antibacterial and antiviral plate has a synergistic effect, and the performance of single antibacterial or antiviral function is increased by 30%. Meanwhile, the antibacterial and antiviral components are more uniformly dispersed in the system through synergistic effect and porous nano structure, and the consumption of effective components is reduced through ion replacement effect, so that the effect of slow release of effective components is achieved, and the antibacterial and antiviral service life is prolonged.

Description

Technical Field

[0001] This invention relates to the field of antibacterial and antiviral board technology, specifically to a composite antibacterial and antiviral board and a method for preparing a composite antibacterial and antiviral agent. Background Technology

[0002] Antibacterial and antiviral boards are boards that inhibit the growth and reproduction of bacteria and viruses. Their technological background stems primarily from people's pursuit of a healthy living environment. With increasing health awareness and concern about the spread of bacteria and viruses in indoor environments, the development of boards with antibacterial and antiviral properties has become an important direction in the materials field. Currently, the research and development of antibacterial and antiviral boards mainly relies on various technologies, such as nano-silver ion technology, which uses nano-sized silver ions uniformly dispersed in the board to disrupt the cell membrane structure of microorganisms and inhibit their growth and reproduction through their strong antibacterial and antiviral properties; natural plant extract technology, which utilizes the antibacterial and antiviral active ingredients of traditional Chinese medicine such as mugwort, isatis root, and honeysuckle, or natural plant extracts such as tea tree oil and allicin, adding them to the board; ion exchange technology, which introduces ions with antibacterial and antiviral effects, such as zinc and copper ions, into the board through ion exchange methods. These ions can affect the physiological functions of microorganisms; and photocatalysis technology, which coats the board surface with photocatalysts such as titanium dioxide, using light conditions to generate strong oxidizing substances that decompose the cell walls and protein structures of bacteria and viruses.

[0003] However, the existing technologies mentioned above have limited antibacterial and antiviral ranges. Different technologies may only be effective against specific types of bacteria or viruses and cannot broadly inhibit a variety of pathogens. Over time, the antibacterial and antiviral effects will continue to weaken, and some coatings may peel off or even detach, leading to a decline in antibacterial and antiviral performance. As a broad-spectrum antibacterial agent, nano silver ions are not effective against all types of bacteria and viruses. Single-ion antibacterial agents have poor wash-off properties and are easily washed off from the surface of the board. After multiple washes, their protective ability will be greatly reduced. The anti-mildew properties of silver ions are also limited. For environments with high requirements for anti-mildew, it is necessary to combine them with other anti-mildew measures or choose materials with better anti-mildew properties. Therefore, we urgently need a composite antibacterial and antiviral board. Summary of the Invention

[0004] To address the shortcomings of the aforementioned technologies, the present invention aims to provide composite antibacterial and antiviral boards and composite antibacterial and antiviral agents. By adding composite reagents with antiviral functions to the impregnation solution prepared by impregnating paper, the antibacterial and antiviral functions are enhanced through the composite of multiple antibacterial ions. Through a porous nanostructure, nanoparticles are encapsulated and more evenly dispersed in the carrier. After pressing, the final formed decorative panel has significant antibacterial and antiviral properties.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a composite antibacterial and antiviral board, comprising two substrates, a balancing layer provided at one end of each of the two substrates, an adhesive provided between each of the two substrates and the two balancing layers, and an antibacterial and antiviral impregnated decorative paper provided between the two balancing layers.

[0006] A composite antibacterial and antiviral board material comprises a composite antibacterial and antiviral agent with the following components: nano-silver-zinc composite ions, polyhexamethylene guanidine hydrochloride, auxiliary antiviral agent, chitosan quaternary ammonium salt, stabilizer propylene glycol, nanoporous aluminosilicate, and solvent deionized water. The proportions of the composite antibacterial and antiviral agent are as follows: nano-silver-zinc composite ion solution, content 2%–5%; polyhexamethylene guanidine hydrochloride, content 10%–20%; auxiliary antiviral agent, chitosan quaternary ammonium salt, content 10%–20%; stabilizer propylene glycol, content 5%–10%; nanoporous aluminosilicate, content 10%–20%; and solvent deionized water, the remainder.

[0007] A method for preparing a nano-silver-zinc composite ionic solution in a composite antibacterial and antiviral board material involves preparing silver nitrate, zinc sulfate, ammonium carbonate, ammonium bicarbonate, deionized water, and anhydrous ethanol to prepare a silver-zinc precursor. Silver nitrate is dissolved in deionized water to obtain a silver nitrate solution, and zinc sulfate is dissolved in deionized water to obtain a zinc sulfate solution. Ammonium carbonate and ammonium bicarbonate are dissolved in deionized water to obtain a precipitate solution. Further, the silver nitrate solution and zinc sulfate solution are slowly added dropwise to the precipitate solution while stirring, reacting to form a silver-zinc precursor precipitate. The silver-zinc precursor precipitate is then subjected to a 3-distillation process using deionized water and anhydrous ethanol. The mixture is washed six times to remove impurities. The washed precipitate is then dried in a vacuum drying oven to obtain dried silver-zinc precursor powder. The dried silver-zinc precursor powder is then added to deionized water and stirred until homogeneous to obtain a silver-zinc precursor solution. This solution is then subjected to ultrasonic treatment to ensure uniform dispersion of the silver-zinc precursor in the solution. The ultrasonically treated silver-zinc precursor solution is then heated to decompose the silver-zinc precursor, generating a nano-silver-zinc composite ion solution. This nano-silver-zinc composite ion solution is then cooled and diluted with deionized water to obtain the desired concentration of nano-silver-zinc composite ion solution.

[0008] A method for preparing polyhexamethylene guanidine hydrochloride in a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board: Hexamethylenediamine and 36% hydrochloric acid are mixed in a certain proportion, the molar ratio of hexamethylenediamine to hydrochloric acid can be controlled between 1:2 and 1:2.5. During the mixing process, hydrochloric acid should be added slowly to avoid violent reaction and local overheating. The mixed solution is heated to an appropriate temperature, controlled between 60-80℃, and the reaction time can be controlled between 3-5 hours. After the reaction is completed, the product is cooled, and then impurities are removed by 3-6 filtrations and 5-10 washings with deionized water. The product is then dried to obtain polyhexamethylene guanidine hydrochloride.

[0009] A method for preparing chitosan quaternary ammonium salt in a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board, wherein chitosan, formaldehyde, formic acid, and distilled water are sequentially added to a three-necked flask equipped with a condenser, wherein the mass ratio of chitosan, formaldehyde, formic acid, and distilled water is 1:5:5:20. A magnetic stirrer is turned on at a speed of 100-700 r / min, and the reaction is carried out at 50-80℃ for 72 hours to obtain a pale yellow solution. The obtained pale yellow solution is then distilled under reduced pressure at 0.05-0.1 MPa and 45-65℃ for 30 min. Then, the pH was adjusted to 10-13 with an alkaline solution to form a large amount of gel. Subsequently, it was vacuum filtered at 0.05-0.1 MPa and washed with anhydrous ethanol until neutral to obtain a pale yellow gel-like substance. After drying at 60-120℃, it was ground into a pale yellow powder. The obtained pale yellow powder was dissolved with an acidic solution, and the pH was adjusted to 3-5 with the addition of acidic solution. At this time, a white precipitate was obtained. It was washed 5-10 times with distilled water and freeze-dried at -30 to -60℃. The dried product was ground to obtain chitosan quaternary ammonium salt.

[0010] A method for preparing nano-aluminosilicate in a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board involves mixing tetraethyl orthosilicate, tetrapropylammonium hydroxide, sodium aluminate, and water in a mass ratio of 45:5:1:120 until homogeneous. The mixture is then placed in a high-temperature hydrothermal reactor, with the volume of the mixture occupying 80%-85% of the total reactor volume. The temperature inside the reactor is raised to 175-185℃ at a heating rate of 4-6℃ / min and held at this temperature for 4-6 hours. After natural cooling, a solid-liquid mixture is obtained. The solid-liquid mixture is centrifuged at 8000-10000 rpm for 5-10 min to obtain a sol clear liquid. The sol clear liquid is spin-coated onto a cleaned glass surface at a spin-coating speed of 2000-3000 rpm. After drying the glass system coated with sol, it is sintered at 500-550℃ for 1-3 h. After natural cooling, a nanoporous aluminosilicate film is obtained. After grinding, nano-aluminosilicate powder is obtained.

[0011] A method for preparing a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board includes the following steps:

[0012] S1. Accurately weigh the prepared nano-silver-zinc composite ion solution, polyhexamethylene guanidine hydrochloride, chitosan quaternary ammonium salt, and nano-aluminosilicate according to the formula ratio.

[0013] S2. Add to an appropriate amount of deionized water and stir at 60-80℃ and a stirring speed of 500-800 r / min for 240-300 minutes to fully dissolve and mix all components.

[0014] S3. Use a thin-film method to filter the prepared composite product to remove impurities;

[0015] S4. The filtered solution is sterilized to obtain the composite antibacterial and antiviral agent product.

[0016] A method for preparing antibacterial and antiviral impregnated decorative paper for composite antibacterial and antiviral boards, wherein the method for preparing the antibacterial and antiviral impregnated decorative paper is as follows:

[0017] S1. Add 5% by weight of curing agent to the melamine-formaldehyde resin for impregnation, which has a solid content of 55% and a pH of 9.5, and stir quickly until homogeneous.

[0018] S2. The decorative paper base paper is driven by the rotating roller shaft of the impregnation machine. The rolling speed of the roller shaft is 15m / min, ensuring that the decorative paper base paper is completely immersed in the first melamine-formaldehyde resin impregnation. It is then transmitted to the drying oven, and the oven temperature is adjusted to 110℃.

[0019] S3. The roller shaft drives the paper to the second impregnation tank. The antibacterial and antiviral agent mentioned above is added to the melamine-formaldehyde resin at a mass ratio of 0.5%. The mixture is quickly stirred evenly to prepare the antibacterial and antiviral melamine-formaldehyde resin for impregnation. The amount of adhesive applied is controlled at 120g to ensure that the decorative paper is completely submerged in the second impregnation. The paper is then driven to the drying oven for a second drying. The oven temperature is 130℃ and the paper is dried for 10 minutes until the pre-curing degree is 40%.

[0020] S4. After the second drying, adjust the oven temperature and dehumidify and cool to 50℃. After two impregnation and drying cycles, the total weight gain rate is controlled at 110% of the original paper. Cut and package according to the required dimensions to obtain antibacterial and antiviral decorative paper.

[0021] A method for preparing a substrate for a composite antibacterial and antiviral board, wherein the method for preparing the substrate is as follows:

[0022] S1. The base material is plywood with a moisture content of 7.5% and a size of 2440mm*1220mm*17mm. The balancing layer is made of engineered wood veneer with a thickness of 0.50mm.

[0023] S2. Using plywood as the base material and engineered wood veneer as the balancing layer, antibacterial and antiviral impregnated paper-faced plywood is prepared using two finishing processes: one-time lamination and two-time lamination.

[0024] S3 一 The double-coating process involves applying a glue applicator to both sides of the plywood, with a glue application rate of 220–230 g / m² on each side. Engineered wood veneers are then pressed onto both sides. The hot-pressing temperature is 125℃, the hot-pressing time is 9–10 min, and the unit hot-pressing pressure is 0.65–0.7 MPa. After hot-pressing, an antibacterial and antiviral impregnated paper veneer is then pressed onto the plywood. The hot-pressing temperature is 125–130℃, the hot-pressing time is 6–7 min, and the unit hot-pressing pressure is 0.60–0.65 MPa.

[0025] S4. The secondary lamination process involves first hot-pressing an antibacterial and antiviral impregnated paper with poplar veneer on one side at a temperature of 190–200℃, a pressure of 2.4 MPa, and a time of 15–20 seconds. Then, a glue machine is used to coat both sides of the plywood with urea-formaldehyde resin, with an application rate of 220–230 g / m² per side. The two layers of the paper / poplar veneer composite are then laminated together at a temperature of 90–95℃, a time of 600 seconds, and a unit pressure of 0.65 MPa.

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0027] This invention combines multiple antibacterial and antiviral technologies to form a novel composite antibacterial and antiviral agent. Compared with general antibacterial or antiviral boards, the aforementioned antibacterial and antiviral boards have a synergistic effect, increasing the performance of single antibacterial or antiviral functions by 30%. At the same time, through synergistic effect and porous nanostructure, this invention allows the antibacterial and antiviral components to be more uniformly dispersed in the system. Meanwhile, through ion replacement, it reduces the consumption of effective components, achieving a sustained release effect of effective components and extending the antibacterial and antiviral efficacy lifespan. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the present invention;

[0029] Figure 2 This is a schematic diagram of the structure of the present invention;

[0030] The components include: 1. Substrate; 2. Balancing layer; 3. Adhesive; 4. Antibacterial and antiviral impregnated decorative paper. Detailed Implementation

[0031] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0032] This invention provides the following technical solutions:

[0033] Example 1

[0034] An embodiment of a composite antibacterial and antiviral agent in a composite antibacterial and antiviral board material.

[0035] Reference Figure 1 ,

[0036] The composite antibacterial and antiviral agent comprises the following components: nano-silver-zinc composite ions, polyhexamethylene guanidine hydrochloride, auxiliary antiviral agent, chitosan quaternary ammonium salt, stabilizer propylene glycol, nanoporous aluminosilicate, solvent deionized water, nano-silver-zinc composite ion solution with a content of 2%–5%, polyhexamethylene guanidine hydrochloride with a content of 10%–20%, auxiliary antiviral agent, chitosan quaternary ammonium salt with a content of 10%–20%, stabilizer propylene glycol with a content of 5%–10%, nanoporous aluminosilicate with a content of 10%–20%, and solvent deionized water, the remaining portion.

[0037] Includes the following steps:

[0038] S1. Accurately weigh the prepared nano-silver-zinc composite ion solution, polyhexamethylene guanidine hydrochloride, chitosan quaternary ammonium salt, and nano-aluminosilicate according to the formula ratio.

[0039] S2. Add to an appropriate amount of deionized water and stir at 60-80℃ and a stirring speed of 500-800 r / min for 240-300 minutes to fully dissolve and mix all components.

[0040] S3. Use a thin-film method to filter the prepared composite product to remove impurities;

[0041] S4. Sterilize the filtered solution to obtain the finished compound antibacterial and antiviral agent.

[0042] The overall steps of the above technical solution are as follows: S1, add 5 parts by mass of 10% nano silver-zinc composite ion solution to 100 parts by mass of deionized water, place it on a magnetic stirrer and mix evenly at a stirring speed of 300 r / min for 15 min until the solution is completely mixed evenly.

[0043] S2. Add hydrochloric acid dropwise to hexamethylenediamine at a molar ratio of 1:2. Heat the mixed liquid to 60°C and react at a constant temperature for 3 hours. After cooling, filter the mixture, wash it with deionized water, and dry it to obtain polyhexamethylene guanidine hydrochloride. Weigh 10 parts by mass of polyhexamethylene guanidine hydrochloride, add sufficient deionized water, and stir continuously until the polyhexamethylene guanidine hydrochloride is completely dissolved.

[0044] S3. Chitosan, formaldehyde, formic acid, and distilled water were sequentially added to a three-necked flask equipped with a condenser. The mass ratio of chitosan, formaldehyde, formic acid, and distilled water was 1:5:5:20. A magnetic stirrer was turned on at 500 rpm, and the reaction was carried out at 50°C for 72 hours. The resulting pale yellow solution was then distilled under reduced pressure at 0.1 MPa and 65°C for 30 minutes. The pH was adjusted to 11 with an alkaline solution to form a large amount of gel. Subsequently, the solution was vacuum filtered at 0.1 MPa. Wash with anhydrous ethanol until neutral to obtain a pale yellow gel-like substance. Dry at 90°C and grind into a pale yellow powder. Dissolve the obtained pale yellow powder with an acidic solution and continue to add acidic solution to adjust to pH 3. At this point, a white precipitate can be obtained. Wash with distilled water 5 times and freeze-dry at -30°C. Grind the dried product to obtain chitosan quaternary ammonium salt. Weigh 10 parts by mass of chitosan quaternary ammonium salt, add sufficient deionized water, and stir continuously until the chitosan quaternary ammonium salt is completely dissolved.

[0045] S4. Tetraethyl orthosilicate, tetrapropylammonium hydroxide, sodium aluminate, and water are mixed evenly in a mass ratio of 45:5:1:120. The mixture is then placed in a high-temperature hydrothermal reactor, with the volume of the mixture occupying 80% of the total reactor volume. The temperature inside the reactor is raised to 175°C at a heating rate of 4°C / min and held for 4 hours. After natural cooling, a solid-liquid mixture is obtained. The solid-liquid mixture is centrifuged at 8000 rpm for 5 minutes to obtain a sol. The sol is then spin-coated onto a clean glass surface at a spin coating speed of 2000 rpm. After drying the glass system coated with the sol, it is sintered at 500°C for 1 hour. After natural cooling, a nanoporous aluminosilicate film is obtained. After grinding, nano-aluminosilicate powder is obtained. 10 parts by mass of the nanoporous aluminosilicate are weighed, and sufficient deionized water is added. The mixture is stirred continuously until the nanoporous aluminosilicate is completely dissolved.

[0046] S5. Add the above-prepared nano-silver-zinc composite ion solution, polyhexamethylene guanidine hydrochloride solution, chitosan quaternary ammonium salt solution, and nano-aluminosilicate solution to an appropriate amount of deionized water, heat to 60°C, stir at 500 r / min for 240 min, filter the prepared composite product using the thin film method to remove impurities, and sterilize the prepared composite solution with ultraviolet radiation at a wavelength of 254 nm for 30 min to obtain the composite antibacterial and antiviral agent.

[0047] S6. Add 5% by mass of curing agent to the melamine-formaldehyde resin used for impregnation, which has a solid content of 55% and a pH of 9.5, and stir quickly until homogeneous.

[0048] S7. The decorative paper base paper is driven by the rotating roller shaft of the impregnation machine. The rolling speed of the roller shaft is 15m / min, ensuring that the decorative paper base paper is completely immersed in the first melamine-formaldehyde resin impregnation. It is then transferred to the drying oven, and the oven temperature is adjusted to 110℃.

[0049] S8. The roller shaft drives the paper to the second impregnation tank. The antibacterial and antiviral agent is added to the melamine-formaldehyde resin at a mass ratio of 0.5%. The mixture is quickly stirred until homogeneous. The amount of adhesive applied is controlled at 120g. The decorative paper is completely submerged during the second impregnation. The paper is then driven to the drying oven for a second drying. The oven temperature is 130℃. The paper is dried for 10 minutes until the pre-curing degree is 40%.

[0050] S9. After the second drying, adjust the oven temperature and dehumidify and cool to 50℃. After two impregnation and drying cycles, the total weight gain rate is controlled at 110% of the original paper. Cut and package according to the required dimensions to obtain antibacterial and antiviral decorative paper.

[0051] S10, made of plywood substrate with a moisture content of 7.5%, with dimensions of 2440mm*1220mm*17mm. The balancing layer is made of engineered wood veneer with a thickness of 0.50mm, and is cured for 7 days.

[0052] S11. Apply glue to both sides of the plywood substrate using a glue applicator, with a glue application rate of 220g / ㎡ on each side. Press engineered wood veneer onto both sides, with a hot-pressing temperature of 125℃, a hot-pressing time of 10min, and a unit hot-pressing pressure of 0.65MPa. After hot-pressing, press antibacterial and antiviral impregnated paper veneer onto the substrate, with a hot-pressing temperature of 136℃, a hot-pressing time of 4min, and a unit hot-pressing pressure of 0.6MPa.

[0053] Example 2

[0054] Example of a nano-silver-zinc composite ion solution in a composite antibacterial and antiviral board material.

[0055] The preparation method of the nano-silver-zinc composite ionic solution is as follows: Prepare silver nitrate, zinc sulfate, ammonium carbonate, ammonium bicarbonate, deionized water, and anhydrous ethanol to prepare the silver-zinc precursor. Dissolve silver nitrate in deionized water to obtain a silver nitrate solution. Dissolve zinc sulfate in deionized water to obtain a zinc sulfate solution. Dissolve ammonium carbonate and ammonium bicarbonate in deionized water to obtain a precipitate solution. Further, slowly add the silver nitrate solution and zinc sulfate solution dropwise to the precipitant solution while stirring. The reaction produces a silver-zinc precursor precipitate. Wash the silver-zinc precursor precipitate 3-6 times with deionized water and anhydrous ethanol to remove impurities. The washed precipitate was then dried in a vacuum drying oven to obtain dried silver-zinc precursor powder. Further, the dried silver-zinc precursor powder was added to deionized water and stirred until homogeneous to obtain a silver-zinc precursor solution. The silver-zinc precursor solution was then subjected to ultrasonic treatment to ensure uniform dispersion of the silver-zinc precursor in the solution. The ultrasonically treated silver-zinc precursor solution was then heated to decompose the silver-zinc precursor, generating a nano-silver-zinc composite ion solution. The generated nano-silver-zinc composite ion solution was cooled and then diluted with deionized water to obtain a nano-silver-zinc composite ion solution of the desired concentration.

[0056] Example 3

[0057] Example of a method for preparing polyhexamethylene guanidine hydrochloride in a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board.

[0058] The preparation method of polyhexamethylene guanidine hydrochloride is as follows: Hexamethylenediamine and 36% hydrochloric acid are mixed in a certain proportion. The molar ratio of hexamethylenediamine to hydrochloric acid can be controlled between 1:2 and 1:2.5. During the mixing process, hydrochloric acid should be added slowly to avoid violent reaction and local overheating. The mixed solution is heated to an appropriate temperature, which is controlled between 60-80℃. The reaction time can be controlled between 3-5 hours. After the reaction is completed, the product is cooled, and then impurities are removed by 3-6 filtrations and 5-10 washings with deionized water. The product is then dried to obtain polyhexamethylene guanidine hydrochloride.

[0059] Example 4

[0060] Example of a method for preparing chitosan quaternary ammonium salt in a composite antibacterial and antiviral board material.

[0061] The preparation method of chitosan quaternary ammonium salt is as follows: Chitosan, formaldehyde, formic acid, and distilled water are added sequentially to a three-necked flask equipped with a condenser. The mass ratio of chitosan, formaldehyde, formic acid, and distilled water is 1:5:5:20. A magnetic stirrer is turned on at a speed of 100-700 r / min, and the reaction is carried out at 50-80℃ for 72 hours to obtain a pale yellow solution. The obtained pale yellow solution is then distilled under reduced pressure at 0.05-0.1 MPa and 45-65℃ for 30 min, and the pH is adjusted with an alkaline solution. 10-13 to form a large amount of gel, then vacuum filtered at 0.05-0.1 MPa, washed with anhydrous ethanol until neutral, to obtain a pale yellow gel-like substance, dried at 60-120℃, ground into a pale yellow powder, dissolved in an acidic solution, and the pH was adjusted to 3-5 by adding more acidic solution, at which point a white precipitate was obtained, washed 5-10 times with distilled water, freeze-dried at -30 to -60℃, and the dried product was ground to obtain chitosan quaternary ammonium salt.

[0062] Example 5

[0063] Example of a method for preparing nano-aluminosilicate in a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board.

[0064] The preparation method of nano-aluminosilicate is as follows: Tetraethyl orthosilicate, tetrapropylammonium hydroxide, sodium aluminate, and water are mixed evenly in a mass ratio of 45:5:1:120. The mixture is then placed in a high-temperature hydrothermal reactor, with the volume of the mixture occupying 80%-85% of the total volume of the reactor. The temperature inside the reactor is raised to 175-185℃ at a heating rate of 4-6℃ / min and held for 4-6 hours. After natural cooling, a solid-liquid mixture is obtained. The solid-liquid mixture is centrifuged at 8000-10000 rpm for 5-10 minutes to obtain a sol. The sol is then spin-coated onto a clean glass surface at a spin-coating speed of 2000-3000 rpm. After drying the glass system coated with the sol, it is sintered at 500-550℃ for 1-3 hours. After natural cooling, a nanoporous aluminosilicate film is obtained. After grinding, nano-aluminosilicate powder is obtained.

[0065] Example 6

[0066] An embodiment of a method for preparing antibacterial and antiviral impregnated decorative paper for composite antibacterial and antiviral boards, wherein the method for preparing antibacterial and antiviral impregnated decorative paper 4 is as follows:

[0067] S1. Add 5% by weight of curing agent to the melamine-formaldehyde resin for impregnation, which has a solid content of 55% and a pH of 9.5, and stir quickly until homogeneous.

[0068] S2. The decorative paper base paper is driven by the rotating roller shaft of the impregnation machine. The rolling speed of the roller shaft is 15m / min, ensuring that the decorative paper base paper is completely immersed in the first melamine-formaldehyde resin impregnation. It is then transmitted to the drying oven, and the oven temperature is adjusted to 110℃.

[0069] S3. The roller shaft drives the paper to the second impregnation tank. The antibacterial and antiviral agent is added to the melamine-formaldehyde resin at a mass ratio of 0.5%. The mixture is quickly stirred evenly to prepare the antibacterial and antiviral melamine-formaldehyde resin for impregnation. The amount of glue applied is controlled at 120g to ensure that the decorative paper is completely submerged in the second impregnation. Then the paper is driven to the drying oven for the second drying. The oven temperature is 130℃ and the paper is dried for 10 minutes until the pre-curing degree is 40%.

[0070] S4. After the second drying, adjust the oven temperature, dehumidify and cool to 50℃. After two impregnation and drying cycles, the total weight gain rate is controlled at 110% of the original paper. Cut and package according to the required size to obtain antibacterial and antiviral decorative paper 4.

[0071] Example 7

[0072] An Example of a Method for Preparing a Substrate for a Composite Antibacterial and Antiviral Board

[0073] It includes two substrates 1, each of which has a balancing layer 2 at one end, an adhesive 3 between each of the two substrates 1 and the two balancing layers 2, and an antibacterial and antiviral impregnated decorative paper 4 between the two balancing layers 2.

[0074] The preparation method of substrate 1 is as follows:

[0075] S1. The base material is plywood with a moisture content of 7.5% and a size of 2440mm*1220mm*17mm. The balance layer 2 is made of engineered wood veneer with a thickness of 0.50mm.

[0076] S2. Using plywood as the base material and engineered wood veneer as the balancing layer, antibacterial and antiviral impregnated paper-faced plywood is prepared using two finishing processes: one-time lamination and two-time lamination.

[0077] S3 一 The double-coating process involves applying a glue applicator to both sides of the plywood, with a glue application rate of 220–230 g / m² on each side. Engineered wood veneers are then pressed onto both sides. The hot-pressing temperature is 125℃, the hot-pressing time is 9–10 min, and the unit hot-pressing pressure is 0.65–0.7 MPa. After hot-pressing, an antibacterial and antiviral impregnated paper veneer is then pressed onto the plywood. The hot-pressing temperature is 125–130℃, the hot-pressing time is 6–7 min, and the unit hot-pressing pressure is 0.60–0.65 MPa.

[0078] S4. The double-layer lamination process involves first hot-pressing an antibacterial and antiviral impregnated paper onto poplar veneer on one side. The hot-pressing temperature is 190–200℃, the hot-pressing pressure is 2.4MPa, and the hot-pressing time is 15–20s. Then, a glue machine coats both sides of the plywood with urea-formaldehyde resin, with an adhesive application rate of 220–230g / ㎡ on each side. The two layers of the paper / poplar veneer composite are then laminated together, with a hot-pressing temperature of 90–95℃, a hot-pressing time of 600s, and a unit hot-pressing pressure of 0.65MPa.

[0079] The preparation method of composite antibacterial and antiviral boards and composite antibacterial and antiviral agents, based on the above technical solutions, includes the following steps;

[0080] S1. Add 3 parts by mass of 10% nano silver-zinc composite ion solution to 100 parts by mass of deionized water, place it on a magnetic stirrer and mix evenly at a stirring speed of 300 r / min for 15 min until the solution is completely mixed.

[0081] S2. Add hexamethylenediamine and 36% hydrochloric acid dropwise to hexamethylenediamine at a molar ratio of 1:2.5. Heat the mixed liquid to 60°C and react at a constant temperature for 3 hours. After cooling, filter the mixture, wash it with deionized water, and dry it to obtain polyhexamethylene guanidine hydrochloride. Weigh 10 parts by mass of polyhexamethylene guanidine hydrochloride, add sufficient deionized water, and stir continuously until the polyhexamethylene guanidine hydrochloride is completely dissolved.

[0082] S3. Chitosan, formaldehyde, formic acid, and distilled water were sequentially added to a three-necked flask equipped with a condenser. The mass ratio of chitosan, formaldehyde, formic acid, and distilled water was 1:5:5:20. A magnetic stirrer was turned on at 500 rpm, and the reaction was carried out at 60°C for 72 hours. The resulting pale yellow solution was then distilled under reduced pressure at 0.1 MPa and 65°C for 30 minutes. The pH was adjusted to 10 with an alkaline solution to form a large amount of gel. Subsequently, the solution was vacuum filtered at 0.1 MPa. Wash with anhydrous ethanol until neutral to obtain a pale yellow gel-like substance. After drying at 90°C, grind it into a pale yellow powder. Dissolve the obtained pale yellow powder with an acidic solution, and continue to add acidic solution to adjust the pH to 3.5. At this point, a white precipitate can be obtained. Wash with distilled water 5 times, freeze dry at -30°C, grind the dried product to obtain chitosan quaternary ammonium salt. Weigh 10 parts by mass of chitosan quaternary ammonium salt, add sufficient deionized water, and stir continuously until the chitosan quaternary ammonium salt is completely dissolved.

[0083] S4. Tetraethyl orthosilicate, tetrapropylammonium hydroxide, sodium aluminate, and water are mixed evenly in a mass ratio of 45:5:1:120. The mixture is then placed in a high-temperature hydrothermal reactor, with the volume of the mixture occupying 70% of the total reactor volume. The temperature inside the reactor is raised to 160°C at a heating rate of 5°C / min and held for 4 hours. After natural cooling, a solid-liquid mixture is obtained. The solid-liquid mixture is centrifuged at 8000 rpm for 5 minutes to obtain a sol-liquid solution. The sol-liquid solution is spin-coated onto a clean glass surface at a spin coating speed of 2000 rpm. After drying the glass system coated with the sol, it is sintered at 500°C for 1 hour. After natural cooling, a nanoporous aluminosilicate film is obtained. After grinding, nano-aluminosilicate powder is obtained. 10 parts by mass of the nanoporous aluminosilicate are weighed, and sufficient deionized water is added. The mixture is stirred continuously until the nanoporous aluminosilicate is completely dissolved.

[0084] S5. Add the above-prepared nano-silver-zinc composite ion solution, polyhexamethylene guanidine hydrochloride solution, chitosan quaternary ammonium salt solution, and nano-aluminosilicate solution to an appropriate amount of deionized water, heat to 50°C, stir at 500 r / min for 200 min, filter the prepared composite product using the thin film method to remove impurities, and sterilize the prepared composite solution with ultraviolet radiation at a wavelength of 254 nm for 60 min to obtain the composite antibacterial and antiviral agent.

[0085] S6. Add 5% by mass of curing agent to the melamine-formaldehyde resin for impregnation, which has a solid content of 55% and a pH of 10, and stir quickly until homogeneous.

[0086] S7. The decorative paper base paper is driven by the rotating roller shaft of the impregnation machine. The rolling speed of the roller shaft is 15m / min, ensuring that the decorative paper base paper is completely immersed in the first melamine-formaldehyde resin impregnation. It is then transferred to the drying oven, and the oven temperature is adjusted to 110℃.

[0087] S8. The roller shaft drives the paper to the second impregnation tank. The antibacterial and antiviral agent is added to the melamine-formaldehyde resin at a mass ratio of 0.5%. The mixture is quickly stirred until homogeneous. The amount of adhesive applied is controlled at 120g. The decorative paper is completely submerged during the second impregnation. The paper is then driven to the drying oven for a second drying at a temperature of 120℃ for 10 minutes until the pre-curing degree is 30%.

[0088] S9. After the second drying, adjust the oven temperature and dehumidify and cool to 55℃. After two impregnation and drying cycles, the total weight gain is controlled at 120% of the original paper. Cut and package according to the required dimensions to obtain antibacterial and antiviral decorative paper.

[0089] S10 uses plywood as the base material with a moisture content of 7.5% and dimensions of 2440mm*1220mm*17mm. The balancing layer uses engineered wood veneer with a thickness of 0.50mm.

[0090] S11. The antibacterial and antiviral impregnated adhesive film paper is hot-pressed onto poplar veneer on one side at a temperature of 190℃, a pressure of 2.4MPa, and a time of 15s. The glue machine coats the plywood with urea-formaldehyde resin on both sides at a rate of 230g / ㎡ per side. The two layers of antibacterial and antiviral adhesive film paper / poplar veneer composite are then pressed together at a temperature of 90℃, a time of 600s, and a pressure of 0.4MPa.

[0091] Comparative example:

[0092] The control sample was a melamine-faced paper-based artificial board prepared using traditional methods. The substrate was plywood with a moisture content of 7.5% and dimensions of 2440mm*1220mm*17mm. The balancing layer was engineered wood veneer with a thickness of 0.50mm. Specifically, untreated decorative paper was pasted onto the untreated substrate.

[0093] The antibacterial and antiviral veneer engineered wood panels prepared in Example 1, Example 7, and the comparative engineered wood panels without antibacterial and antiviral treatment were subjected to antibacterial and antiviral tests. The test results are shown in the table below:

[0094] Table 1

[0095]

[0096]

[0097]

[0098] Table 2

[0099]

[0100]

[0101] The results of the antibacterial performance test are shown in the table below.

[0102] Table 3

[0103]

[0104] Data from Tables 1, 2, and 3 show that Examples 1 and 2 exhibit excellent antibacterial and antiviral effects, achieving an antibacterial rate of 99.99% against the three tested bacteria. The antiviral efficacy against human coronavirus and human influenza virus is also above 99%. In conclusion, the described antibacterial and antiviral board material demonstrates good inhibitory and killing effects against bacteria and viruses, while the untreated board material showed virtually no inhibitory or killing effect on the tested bacteria and viruses.

[0105] This invention combines multiple antibacterial and antiviral technologies to form a novel composite antibacterial and antiviral agent. Compared with general antibacterial or antiviral boards, the aforementioned antibacterial and antiviral boards have a synergistic effect, increasing the performance of single antibacterial or antiviral functions by 30%. At the same time, through synergistic effect and porous nanostructure, this invention allows the antibacterial and antiviral components to be more uniformly dispersed in the system. Meanwhile, through ion replacement, it reduces the consumption of effective components, achieving a sustained release effect of effective components and extending the antibacterial and antiviral efficacy lifespan.

[0106] Although specific 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 specific embodiments without departing from the principles and spirit, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A composite antibacterial and antiviral panel, characterized in that, The application relates to a composite antibacterial and antiviral plate, which comprises two substrates (1), the two substrates (1) are provided with balance layers (2) at one end, adhesive (3) is arranged between the two substrates (1) and the two balance layers (2), and an antibacterial and antiviral impregnated decorative paper (4) is arranged between the two balance layers (2). The ratio of the composite antibacterial and antiviral agent of the composite antibacterial and antiviral plate is as follows: the composite antibacterial and antiviral agent comprises the following components: nano silver-zinc composite ions, polyhexamethylene guanidine hydrochloride, chitosan quaternary ammonium salt, a stabilizer propylene glycol, nano porous structure aluminosilicate and deionized water; the ratio of the composite antibacterial and antiviral agent is as follows: the content of the nano silver-zinc composite ion solution is 2-5%, the content of the polyhexamethylene guanidine hydrochloride is 10-20%, the content of the chitosan quaternary ammonium salt is 10-20%, the content of the stabilizer propylene glycol is 5-10%, the content of the nano porous structure aluminosilicate is 10-20%, and the content of the deionized water is the remaining part.

2. The composite antibacterial and antiviral panel according to claim 1, characterized in that: The preparation method of the nano silver-zinc composite ion solution in the composite antibacterial and antiviral agent is as follows: silver nitrate, zinc sulfate, ammonium carbonate, ammonium bicarbonate, deionized water and anhydrous ethanol are prepared, a silver-zinc precursor is prepared, silver nitrate is dissolved in deionized water to obtain a silver nitrate solution, zinc sulfate is dissolved in deionized water to obtain a zinc sulfate solution, ammonium carbonate and ammonium bicarbonate are dissolved in deionized water to obtain a precipitant solution, the silver nitrate solution and the zinc sulfate solution are slowly added into the precipitant solution while stirring, a silver-zinc precursor precipitate is generated, the silver-zinc precursor precipitate is washed with deionized water and anhydrous ethanol for 3-6 times to remove impurities, and then the washed precipitate is dried in a vacuum drying box to obtain dry silver-zinc precursor powder; the dry silver-zinc precursor powder is added into deionized water and uniformly stirred to obtain a silver-zinc precursor solution; the silver-zinc precursor solution is ultrasonically treated to uniformly disperse the silver-zinc precursor in the solution; the ultrasonically treated silver-zinc precursor solution is heated to decompose the silver-zinc precursor and generate a nano silver-zinc composite ion solution; the generated nano silver-zinc composite ion solution is cooled and then diluted with deionized water to obtain a nano silver-zinc composite ion solution with a required concentration.

3. The composite antibacterial and antiviral panel according to claim 1, characterized in that: The preparation method of the polyhexamethylene guanidine hydrochloride in the composite antibacterial and antiviral agent is as follows: hexamethylene diamine and 36% hydrochloric acid are mixed at a certain ratio, the molar ratio of the hexamethylene diamine to the hydrochloric acid is controlled to be 1:2-1:2.5, the hydrochloric acid is slowly added during the mixing process to avoid violent reaction and local overheating, the mixed solution is heated to an appropriate temperature, the temperature is controlled to be 60-80 DEG C, the reaction time is controlled to be 3-5 hours, after the reaction is completed, the product is cooled, impurities are removed through 3-6 times of suction filtration and 5-10 times of deionized water washing, and the product is dried to obtain polyhexamethylene guanidine hydrochloride.

4. The composite antimicrobial and antiviral panel of claim 1, wherein: The preparation method of the chitosan quaternary ammonium salt in the composite antibacterial and antiviral agent is as follows: chitosan, formaldehyde, formic acid and distilled water are sequentially added into a three-necked flask provided with a condenser, wherein the mass ratio of chitosan, formaldehyde, formic acid and distilled water is 1:5:5:20, a magnetic stirrer is started, the rotating speed is 100-700 r / min, the reaction is carried out at 50-80 ℃ for 72 hours, a light yellow solution is obtained, the light yellow solution is distilled under reduced pressure at 0.05-0.1 MPa and 45-65 ℃ for 30 min, then a large amount of gel is formed by adjusting the pH to 10-13 with an alkaline solution, then vacuum filtration is carried out at 0.05-0.1 MPa, the gel is washed with anhydrous ethanol until neutral, a light yellow gel-like substance is obtained, the light yellow gel-like substance is dried at 60-120 ℃, then ground into a light yellow powder, the light yellow powder is dissolved in an acidic solution, the pH is adjusted to 3-5 by continuously adding the acidic solution, then a white precipitate is obtained, the white precipitate is washed with distilled water for 5-10 times, and the product after drying is ground to obtain the chitosan quaternary ammonium salt.

5. The composite antimicrobial and antiviral panel of claim 1, wherein: The preparation method of the nano-porous structure aluminosilicate in the composite antibacterial and antiviral agent is as follows: tetraethyl orthosilicate, tetrapropylammonium hydroxide, sodium metaaluminate and water are uniformly stirred and mixed according to a mass ratio of 45:5:1:120, then the mixed system is placed in a high-temperature hydrothermal reaction kettle, wherein the volume of the mixed system accounts for 80%-85% of the total volume of the reaction kettle, the temperature in the reaction kettle is raised to 175-185 ℃ at a temperature rising rate of 4-6 ℃ / min, and the reaction is carried out for 4-6 h, then the solid-liquid mixed system is obtained after natural cooling, the solid-liquid mixed system is centrifuged at a rotating speed of 8000-10000 rpm for 5-10 min to obtain a sol clear liquid, the sol clear liquid is spin-coated on a cleaned glass surface at a spin-coating speed of 2000-3000 rpm, the glass system coated with the sol is dried, then sintered at 500-550 ℃ for 1-3 h, and the nano-porous aluminosilicate film is obtained after natural cooling, and the nano-porous structure aluminosilicate powder is obtained after grinding.

6. The composite antimicrobial and antiviral panel of claim 1, wherein: The preparation method of the antibacterial and antiviral impregnated decorative paper (4) is as follows: S1, a melamine formaldehyde resin with a solid content of 55% and a pH of 9.5 is used for impregnation, and a curing agent with a mass ratio of 5% is added and uniformly stirred rapidly; S2, the decorative paper base paper is driven to rotate by the rotating roller shaft of the impregnation machine, the rolling shaft runs at a linear speed of 15 m / min, and the decorative paper base paper is completely immersed in the first melamine formaldehyde resin impregnation, and then is transmitted to a drying oven with an oven temperature of 110 ℃; S3, the rolling shaft is transmitted to the second impregnation tank, the composite antibacterial and antiviral agent is added to the melamine formaldehyde resin with a mass ratio of 0.5%, and the antibacterial and antiviral melamine formaldehyde resin for impregnation is uniformly stirred rapidly, the glue amount is controlled to be 120 g, the decorative paper is completely immersed in the second impregnation, and then is transmitted to the drying oven for the second drying, the oven temperature is 130 ℃, and the drying time is 10 min to obtain a pre-curing degree of 40%. S4, after the second drying, adjust the oven temperature, and cool to 50℃, the total weight gain rate is controlled at 110% of the original paper after two times of impregnation and drying, cut and package according to the required size, and obtain the antibacterial and antiviral impregnated decorative paper (4).

7. The composite antimicrobial and antiviral panel of claim 1, wherein: The preparation method of the substrate (1) is: S1, select the fine wood board substrate, the moisture content is 7.5%, the specification is 2440mm*1220mm*17mm, and the balancing layer (2) is selected as the technology wood veneer with a thickness of 0.50mm; S2, using the fine wood board as the substrate and the technology wood veneer as the balancing layer, the antibacterial and antiviral impregnated veneer core board is prepared by using one-time coating method and two-time coating method; S3, one-time coating method, using the cloth coating machine to coat the fine wood board on both sides, the coating amount of each side is 220~230g / ㎡, and the technology wood veneer is pressed on the upper and lower surfaces, the hot pressing temperature is 125℃, the hot pressing time is 9~10min, and the unit hot pressing pressure is 0.65~0.7MPa; after hot pressing, the antibacterial and antiviral impregnated veneer core board is pressed, the hot pressing temperature is 125~130℃, the hot pressing time is 6~7min, and the unit hot pressing pressure is 0.60~0.65MPa; S4, two-time coating method, first, the antibacterial and antiviral impregnated veneer core board is hot pressed with the poplar veneer on one side, the hot pressing temperature is 190~200℃, the hot pressing pressure is 2.4MPa, and the hot pressing time is 15~20s; the cloth coating machine is used to coat the fine wood board on both sides with urea-formaldehyde resin, the coating amount of each side is 220~230g / ㎡, and the veneer / poplar veneer composite is pressed on the upper and lower layers, the hot pressing temperature is 90~95℃, the hot pressing time is 600s, and the unit hot pressing pressure is 0.65MPa.

8. A method for preparing a composite antibacterial and antiviral agent for a composite antibacterial and antiviral board as described in claim 1, characterized in that: The method comprises the following steps: S1, accurately weigh the prepared nano-silver-zinc composite ion solution, polyhexamethylene guanidine hydrochloride, chitosan quaternary ammonium salt, and nano-porous aluminum silicate according to the formula proportion; S2, add to an appropriate amount of ion water, stir at 60~80℃ and a stirring speed of 500~800r / min for 240~300min to fully dissolve and mix the components; S3, use the film method to filter the prepared composite product to remove impurities; S4, sterilize the filtered solution to obtain the finished product of the composite antibacterial and antiviral agent.

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