Negative oxygen ion antibacterial plate

Abstract

The application discloses a kind of negative oxygen ion antibacterial plate, including plate base layer and negative oxygen ion antibacterial layer, the negative oxygen ion antibacterial layer is prepared by including the following raw materials: photocuring resin, HDDA monomer, photoinitiator, leveling wetting agent, foam inhibitor, functional adhesive;Wherein, the functional adhesive is prepared by the following raw materials: polyurethane modified acrylate adhesive, negative oxygen ion antibacterial composite powder, chitosan quaternary ammonium salt, sodium polyacrylate, sodium polyphosphate, dodecyl phenol polyoxyethylene and silane coupling agent;The negative oxygen ion antibacterial composite powder includes inorganic antibacterial agent and negative oxygen ion mineral powder.The negative oxygen ion antibacterial plate of the application has high negative oxygen ion concentration, and the stability and durability of negative oxygen ion release efficiency are good, and the synergy of antibacterial and purification function is good, with excellent antibacterial and antiviral efficacy.

Description

Technical Field

[0001] This invention relates to a negative ion antibacterial board, belonging to the technical field of building sound and heat insulation boards. Background Technology

[0002] Calcium silicate boards and magnesium oxide boards, among other building materials, are widely used in interior decoration, furniture, and flooring due to their excellent sound insulation, heat insulation, thermal insulation properties, high tensile strength, and aging resistance. To meet people's demands for healthy indoor environments, current technologies primarily achieve antibacterial functions by applying an antibacterial coating, such as a silver ion coating or a zinc oxide film layer, to the surface of these boards. However, as people's requirements for healthy indoor environments continue to increase, the shortcomings of these antibacterial coatings in terms of antibacterial performance are becoming increasingly prominent: 1) Antibacterial coatings such as silver ion coatings and zinc oxide film layers can only inhibit microorganisms in direct contact and cannot purify or remove bacteria and viruses suspended in the air; 2) The antibacterial layer is easily damaged by friction or washing, leading to a decrease in antibacterial effectiveness and poor antibacterial durability.

[0003] In addition, the application of negative ion antibacterial layers in boards is gradually increasing, but existing negative ion boards also have certain shortcomings: 1) Poor stability of negative ion release efficiency: Affected by conditions such as temperature and humidity, high temperature and high humidity result in rapid release, while low temperature and low humidity result in slow release, leading to uneven concentration of negative ions and poor antibacterial effect during application; 2) Poor synergy between antibacterial and purification functions: Negative ion antibacterial layers have a certain inhibitory effect on Escherichia coli and Staphylococcus aureus, but the inhibition rate is relatively low, and the effect on fungi (such as mold) is very poor, as they cannot decompose metabolic products.

[0004] Therefore, the present invention provides a negative oxygen ion antibacterial board that has both high negative oxygen ion concentration and antibacterial and antiviral effects. Summary of the Invention

[0005] At least to address one of the problems existing in the prior art, the present invention provides a negative ion antibacterial board with a high concentration of negative ions, good stability and durability of negative ion release efficiency, and good synergy between antibacterial and purification functions, thus exhibiting excellent antibacterial and antiviral effects.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a negative ion antibacterial board, comprising a board base layer and a negative ion antibacterial layer, wherein the negative ion antibacterial layer is prepared from raw materials comprising the following parts by weight: 30-45 parts of photocurable resin, 35-50 parts of HDDA monomer, 2.5-3.5 parts of photoinitiator, 0.3-0.5 parts of leveling and wetting agent, 0.5-0.6 parts of antifoaming agent, and 10-15 parts of functional adhesive;

[0007] The functional adhesive is prepared from the following raw materials in parts by weight: 60-70 parts of polyurethane modified acrylate adhesive, 20-30 parts of negative oxygen ion antibacterial composite powder, 5-8 parts of chitosan quaternary ammonium salt, 2-4 parts of sodium polyacrylate, 0-0.04 parts of sodium polyphosphate, 1-2 parts of dodecylphenol polyoxyethylene ether, and 3-5 parts of silane coupling agent.

[0008] Preferably, the negative oxygen ion antibacterial composite powder comprises an inorganic antibacterial agent and negative oxygen ion mineral powder.

[0009] Preferably, in the negative oxygen ion antibacterial composite powder, the negative oxygen ion mineral powder is pretreated by calcination and / or plasma technology.

[0010] Preferably, in the negative oxygen ion antibacterial composite powder, the negative oxygen ion mineral powder is pretreated by calcination and plasma technology.

[0011] Preferably, in the negative oxygen ion antibacterial composite powder, the mass ratio of negative oxygen ion mineral powder to inorganic antibacterial agent is 2~2.5:1.

[0012] Preferably, in the negative oxygen ion antibacterial composite powder, the negative oxygen ion mineral powder is composed of zeolite micron powder, tourmaline submicron powder, purple jade submicron powder and red ochre submicron powder.

[0013] Preferably, in the negative oxygen ion mineral powder, the mass ratio of zeolite micron powder, tourmaline submicron powder, purple jade submicron powder and red ochre submicron powder is 3:6~8:1~2:3~4.

[0014] Preferably, in the negative ion antibacterial composite powder, the inorganic antibacterial agent is composed of zinc oxide and silver.

[0015] Preferably, in the inorganic antibacterial agent, the mass ratio of zinc oxide to silver is 8~10:1.

[0016] Preferably, in the functional adhesive, chitosan quaternary ammonium salt is coated on the surface of the negative oxygen ion antibacterial composite powder.

[0017] Preferably, the negative oxygen ion antibacterial composite powder is an inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder.

[0018] Preferably, the particle size of the inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder is 0.1~2μm.

[0019] Preferably, the inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder is prepared from negative oxygen ion mineral powder, zinc nitrate, silver nitrate, ethanol aqueous solution, citric acid, and ammonia water as raw materials through sol-gel method, drying, initial grinding, sintering, and grinding.

[0020] Preferably, in the preparation of inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, the drying is supercritical drying.

[0021] Preferably, in the preparation of inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, the sintering conditions are to gradually increase the temperature to 470-500℃ at a rate of 1~2℃ / min and then hold it at that temperature for sintering.

[0022] Preferably, the preparation method of the functional adhesive includes the following steps:

[0023] (1) Dissolve chitosan quaternary ammonium salt in an ethanol aqueous solution with pH 6-7 to form a 1.5-2% chitosan quaternary ammonium salt solution, then add a small amount of dodecylphenol polyoxyethylene ether and negative oxygen ion antibacterial composite powder, stir and disperse evenly to form a uniform suspension, then add sodium polyphosphate, stir evenly, heat to 60-65℃ and stir for 2-3 hours to coat the surface of the negative oxygen ion antibacterial composite powder with chitosan quaternary ammonium salt, filter and dry to obtain negative oxygen ion antibacterial composite powder coated with chitosan quaternary ammonium salt;

[0024] (2) Add sodium polyacrylate to polyurethane modified acrylate adhesive, stir until completely dissolved, then add dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0025] (3) Mix the chitosan quaternary ammonium salt-coated negative oxygen ion antibacterial composite powder with silane coupling agent and stir evenly, then add it to the uniform base liquid and stir to disperse evenly to obtain a functional adhesive.

[0026] Preferably, the preparation method of the inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder is as follows:

[0027] Step 1: First, calcine the negative oxygen ion mineral powder at 600~650℃ for 2~3 hours, and then use plasma technology to activate the calcined negative oxygen ion mineral powder to make its surface rich in active groups, thus obtaining pretreated negative oxygen ion mineral powder.

[0028] Step 2: Dissolve zinc nitrate and silver nitrate in an ethanol aqueous solution and stir until completely dissolved to form a transparent mixture with a zinc ion concentration of 0.025~0.03M and a silver ion concentration of 0.0023M.

[0029] Step 3: Mix the pretreated negative oxygen ion mineral powder with the transparent mixture and sonicate it to disperse it evenly and form a uniform suspension. Adjust the pH to 6-8 with ammonia water, then add citric acid and stir to form a stable sol. Heat the mixture to 60-65℃ to form a transparent sol, and then let it stand to completely gel, thus obtaining a wet gel. The molar amount of citric acid added is the sum of the total molar amounts of zinc ions and silver ions.

[0030] (4) Dry the wet gel to form a dry gel, then grind the dry gel to a particle size greater than 200 mesh, and then gradually heat it to 470~500℃ at a rate of 1~2℃ / min for sintering. After natural cooling, grind it to a particle size of 0.1~2μm to obtain inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder.

[0031] Preferably, the preparation method of the negative ion antibacterial board is as follows: after mixing the light-curing resin, HDDA monomer, photoinitiator, leveling and wetting agent, antifoaming agent and functional adhesive evenly, the mixture is coated onto the surface of the substrate of the board. After ultraviolet curing, a negative ion antibacterial layer is formed on the surface of the substrate of the board, thus obtaining the negative ion antibacterial board.

[0032] Preferably, the substrate of the board is one of calcium silicate board, magnesium oxide board, etc.

[0033] The beneficial effects of this invention are as follows: The negative ion antibacterial board of this invention is provided with a negative ion antibacterial layer, which can generate a high concentration of negative ions, achieving antibacterial, antiviral, and antifungal effects; the negative ion antibacterial layer of this invention uses a functional adhesive containing polyurethane-modified acrylate adhesive, negative ion antibacterial composite powder, chitosan quaternary ammonium salt, etc., which not only enhances the stability of the functional adhesive in the negative ion antibacterial layer, but also improves the antibacterial, antiviral efficacy and durability; the functional adhesive of this invention uses an inorganic antibacterial agent-negative ion mineral powder-chitosan quaternary ammonium salt composite synergistic effect. This invention effectively improves the removal rate of airborne bacteria and viruses to 99.9%, while also exhibiting excellent removal effects on mold, demonstrating good synergy between antibacterial and purification functions. The invention utilizes a composite of inorganic antibacterial agent, negative oxygen ion mineral powder, and chitosan quaternary ammonium salt to form a multi-layered structure. These components work synergistically to improve the stability of negative oxygen ion release efficiency. Even under the influence of temperature and humidity, the concentration of negative oxygen ions maintains good uniformity and stability, resulting in superior antibacterial and antiviral effects during application. This further enhances the durability of the negative oxygen ion antibacterial layer in antibacterial and antiviral properties. Detailed Implementation

[0034] The following is a clear and complete description of the technical solutions in the implementation of this invention. The described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents, instruments, or components used that do not specify the manufacturer are all conventional products that can be purchased commercially.

[0035] The polyurethane-modified acrylate adhesive used in this invention is a polyurethane-modified acrylate water-based adhesive, purchased from Shanghai Snow New Materials Co., Ltd., with a formulation of 100 parts by weight of acrylate, 10-20 parts by weight of polyurethane, and appropriate amounts of peroxide initiator, emulsifier, acrylic acid, water, and N-hydroxymethylacrylamide.

[0036] Preparation Example 1

[0037] A method for preparing a functional adhesive, the specific process of which is as follows:

[0038] (1) Add 3 parts of sodium polyacrylate to 65 parts of polyurethane modified acrylate adhesive, stir until completely dissolved, then add 1.5 parts of dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0039] (2) Mix 24.5 parts of negative oxygen ion antibacterial composite powder, 6.5 parts of hydroxypropyltrimethylammonium chloride chitosan and 4 parts of silane coupling agent KH550 evenly, add them to the above uniform base liquid, stir and disperse evenly to obtain functional adhesive;

[0040] The negative ion antibacterial composite powder contains 17.5 parts of negative ion mineral powder and 7 parts of inorganic antibacterial agent. The negative ion mineral powder consists of 3.5 parts of 1~5μm zeolite micron powder, 8.17 parts of tourmaline submicron powder, 1.75 parts of purple jade submicron powder and 4.08 parts of red ochre submicron powder. The inorganic antibacterial agent consists of 6.3 parts of nano zinc oxide and 0.7 parts of nano silver.

[0041] Preparation Example 2

[0042] A method for preparing a functional adhesive, the specific process of which is as follows:

[0043] (1) Add 2 parts of sodium polyacrylate to 60 parts of polyurethane modified acrylate adhesive, stir until completely dissolved, then add 1 part of dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0044] (2) Mix 20 parts of negative oxygen ion antibacterial composite powder, 8 parts of hydroxypropyltrimethylammonium chloride chitosan and 3 parts of silane coupling agent KH550 evenly, add them to the above uniform base liquid, stir and disperse evenly to obtain functional adhesive.

[0045] The negative ion antibacterial composite powder contains 13.4 parts of negative ion mineral powder and 6.6 parts of inorganic antibacterial agent. The negative ion mineral powder consists of 2.5125 parts of 1~5μm zeolite micron powder, 5.8625 parts of tourmaline submicron powder, 1.675 parts of purple jade submicron powder and 2.5125 parts of red ochre submicron powder. The inorganic antibacterial agent consists of 5.87 parts of nano zinc oxide and 0.73 parts of nano silver.

[0046] Preparation Example 3

[0047] A method for preparing a functional adhesive, the specific process of which is as follows:

[0048] (1) Add 4 parts of sodium polyacrylate to 70 parts of polyurethane modified acrylate adhesive, stir until completely dissolved, then add 2 parts of dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0049] (2) Mix 30 parts of negative oxygen ion antibacterial composite powder, 5 parts of hydroxypropyltrimethylammonium chloride chitosan and 5 parts of silane coupling agent KH550 evenly, add them to the above uniform base liquid, stir and disperse evenly to obtain functional adhesive.

[0050] The negative ion antibacterial composite powder contains 20.9 parts of negative ion mineral powder and 9.1 parts of inorganic antibacterial agent. The negative ion mineral powder consists of 4.49 parts of 1~5μm zeolite micron powder, 8.96 parts of tourmaline submicron powder, 1.49 parts of purple jade submicron powder and 5.96 parts of red ochre submicron powder. The inorganic antibacterial agent consists of 8.27 parts of nano zinc oxide and 0.83 parts of nano silver.

[0051] Preparation Example 4

[0052] A method for preparing a functional adhesive differs from the method in Preparation Example 1 in that: a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. The pretreated negative ion antibacterial composite powder is prepared by first calcining 17.5 parts of negative ion mineral powder at 620°C for 2.5 hours, and then mixing it evenly with 7 parts of inorganic antibacterial agent. The rest is completely the same as in Preparation Example 1.

[0053] Preparation Example 5

[0054] A method for preparing a functional adhesive differs from that in Preparation Example 1 in that: a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. The pretreated negative ion antibacterial composite powder is prepared by first activating 17.5 parts of negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, and then mixing it evenly with 7 parts of inorganic antibacterial agent; the rest is completely the same as in Preparation Example 1.

[0055] Preparation Example 6

[0056] A method for preparing a functional adhesive differs from that in Preparation Example 1 in that: a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. This pretreated negative ion antibacterial composite powder is prepared by first calcining 17.5 parts of negative ion mineral powder at 620°C for 2.5 hours, then activating the calcined negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, and then mixing it evenly with 7 parts of inorganic antibacterial agent. The rest is completely the same as in Preparation Example 1.

[0057] Preparation Example 7

[0058] A method for preparing a functional adhesive differs from that in Preparation Example 1 in that:

[0059] (1) Dissolve 6.5 parts of hydroxypropyltrimethylammonium chloride chitosan in an ethanol aqueous solution with a volume ratio of 1:1 at pH 6~7 to form a 2% chitosan quaternary ammonium salt solution. Then add 0.07 parts of a small amount of dodecylphenol polyoxyethylene ether and 24.5 parts of negative oxygen ion antibacterial composite powder. Stir and disperse evenly to form a uniform suspension. Then add 0.03 parts of sodium polyphosphate. After stirring evenly, heat to 60~65℃ and stir for 2.5h to coat the surface of the negative oxygen ion antibacterial composite powder with chitosan quaternary ammonium salt. Filter and dry to obtain the negative oxygen ion antibacterial composite powder coated with chitosan quaternary ammonium salt.

[0060] (2) Add 3 parts of sodium polyacrylate to 65 parts of polyurethane modified acrylate adhesive, stir until completely dissolved, then add 1.43 parts of dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0061] (3) Mix the chitosan quaternary ammonium salt-coated negative oxygen ion antibacterial composite powder and 4 parts of silane coupling agent KH550 evenly, add them to the above uniform base liquid, stir and disperse evenly to obtain a functional adhesive; the rest is exactly the same as in preparation example 1.

[0062] Preparation Example 8

[0063] A method for preparing a functional adhesive is as follows: the steps are the same as in Example 7, except that a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. The pretreated negative ion antibacterial composite powder is prepared by first calcining 17.5 parts of negative ion mineral powder at 620°C for 2.5 hours, and then mixing it evenly with 7 parts of inorganic antibacterial agent; the rest is completely the same as in Example 7.

[0064] Preparation Example 9

[0065] A method for preparing a functional adhesive differs from the steps in Preparation Example 7 in that: a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. The pretreated negative ion antibacterial composite powder is prepared by first activating 17.5 parts of negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, and then mixing it evenly with 7 parts of inorganic antibacterial agent; the rest is completely the same as in Preparation Example 7.

[0066] Preparation Example 10

[0067] A method for preparing a functional adhesive differs from that in Preparation Example 7 in that: a pretreated negative ion antibacterial composite powder is used instead of the original negative ion antibacterial composite powder. This pretreated negative ion antibacterial composite powder is prepared by first calcining 17.5 parts of negative ion mineral powder at 620°C for 2.5 hours, then activating the calcined negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, and then mixing it evenly with 7 parts of inorganic antibacterial agent. The rest is completely the same as in Preparation Example 7.

[0068] Preparation Example 11

[0069] A method for preparing a functional adhesive differs from that in Preparation Example 1 in that:

[0070] (1) Dissolve 14.659 parts of zinc nitrate and 1.103 parts of silver nitrate in an ethanol aqueous solution with a volume ratio of 1:1, stir until completely dissolved, and form a transparent mixed solution with a zinc ion concentration of 0.0275M and a silver ion concentration of 0.0023M;

[0071] (2) Mix 17.5 parts of negative oxygen ion mineral powder with transparent mixed liquid and sonicate to disperse evenly and form a uniform suspension. Adjust the pH to 6-8 with ammonia water, then add 16.1 parts of citric acid and stir to form a stable sol. Heat to 60-65℃ to form a transparent sol, and then let stand to completely gel to obtain a wet gel.

[0072] Among them, the negative oxygen ion mineral powder consists of 3.5 parts of 1~5μm zeolite micron powder, 8.17 parts of tourmaline submicron powder, 1.75 parts of purple jade submicron powder and 4.08 parts of red ochre submicron powder;

[0073] (3) The wet gel is dried in an oven at 60~65℃ under normal pressure for 10h to form a dry gel. The dry gel is then initially ground to a particle size greater than 200 mesh. The temperature is then gradually increased to 495℃ at a rate of 1~2℃ / min for sintering and holding for 2h. After natural cooling, it is ground to a particle size of 0.1~2μm to obtain inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, namely negative oxygen ion antibacterial composite powder.

[0074] The inorganic antibacterial agent consists of 6.3 parts nano zinc oxide and 0.7 parts nano silver.

[0075] (4) Dissolve 6.5 parts of hydroxypropyltrimethylammonium chloride chitosan in an ethanol aqueous solution with a volume ratio of 1:1 at pH 6-7 to form a 2% chitosan quaternary ammonium salt solution. Then add 0.07 parts of a small amount of dodecylphenol polyoxyethylene ether and the above negative oxygen ion antibacterial composite powder, stir and disperse evenly to form a uniform suspension. Then add 0.03 parts of sodium polyphosphate, stir evenly, heat to 60-65℃ and stir for 2.5h to coat the surface of the negative oxygen ion antibacterial composite powder with chitosan quaternary ammonium salt. Filter and dry to obtain the negative oxygen ion antibacterial composite powder coated with chitosan quaternary ammonium salt.

[0076] (5) Add 3 parts of sodium polyacrylate to 65 parts of polyurethane modified acrylate adhesive, stir until completely dissolved, then add 1.43 parts of dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid.

[0077] (6) Mix the above-mentioned chitosan quaternary ammonium salt-coated negative oxygen ion antibacterial composite powder and 4 parts of silane coupling agent KH550 evenly, add them to the above-mentioned uniform base liquid, stir and disperse evenly to obtain a functional adhesive.

[0078] Preparation Example 12

[0079] A method for preparing a functional adhesive, which is similar to the steps in Preparation Example 11, is as follows: Step (3) the wet gel is placed in a high-pressure reactor and supercritically dried for 4 hours at 220°C and 5-8 MPa using ethanol as the supercritical fluid to obtain a loose and porous dry gel. The dry gel is then initially ground to a particle size greater than 200 mesh, and then sintered at 495°C at a rate of 1-2°C / min for 2 hours. After natural cooling, it is ground again to a particle size of 0.1-2 μm to obtain an inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, i.e., negative oxygen ion antibacterial composite powder; the rest is completely the same as in Preparation Example 11.

[0080] Preparation Example 13

[0081] A method for preparing a functional adhesive differs from that in Preparation Example 11 in that: a pretreated negative ion mineral powder is used instead of the original negative ion mineral powder. The pretreated negative ion mineral powder is prepared by first calcining 17.5 parts of the negative ion mineral powder at 620°C for 2.5 hours, and then activating the calcined negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, thereby obtaining the pretreated negative ion mineral powder. The rest is completely the same as in Preparation Example 11.

[0082] Preparation Example 14

[0083] A method for preparing a functional adhesive differs from that in Preparation Example 12 in that: a pretreated negative ion mineral powder is used instead of the original negative ion mineral powder. The pretreated negative ion mineral powder is obtained by calcining 17.5 parts of the original negative ion mineral powder at 620°C for 2.5 hours. The rest is completely the same as in Preparation Example 12.

[0084] Preparation Example 15

[0085] A method for preparing a functional adhesive differs from the steps in Preparation Example 12 in that: a pretreated negative ion mineral powder is used instead of the original negative ion mineral powder. The pretreated negative ion mineral powder is prepared by first activating 17.5 parts of the calcined negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, thereby obtaining the pretreated negative ion mineral powder. The rest is completely the same as in Preparation Example 12.

[0086] Preparation Example 16

[0087] A method for preparing a functional adhesive differs from that in Preparation Example 12 in that: a pretreated negative ion mineral powder is used instead of the original negative ion mineral powder. The pretreated negative ion mineral powder is prepared by first calcining 17.5 parts of the negative ion mineral powder at 620°C for 2.5 hours, and then activating the calcined negative ion mineral powder using plasma technology to enrich its surface with active hydroxyl groups, thereby obtaining the pretreated negative ion mineral powder. The rest is completely the same as in Preparation Example 12.

[0088] Preparation Example 17

[0089] A method for preparing a functional adhesive, which is similar to the steps in Preparation Example 16, is as follows: the pretreated negative oxygen ion mineral powder is prepared by first calcining 17.5 parts of negative oxygen ion mineral powder at 620°C for 2.5 hours, and then activating the calcined negative oxygen ion mineral powder using plasma technology to enrich its surface with active amino groups, thereby obtaining pretreated negative oxygen ion mineral powder; the rest is completely the same as in Preparation Example 16.

[0090] Example 1

[0091] A negative oxygen ion antibacterial board and its preparation method are as follows:

[0092] After mixing 38 parts of UV-curable resin, 42 parts of HDDA monomer, 3 parts of photoinitiator, 0.4 parts of leveling and wetting agent, 0.55 parts of antifoaming agent, and 12.5 parts of the functional adhesive of Preparation Example 1, the mixture was applied to the surface of the calcium silicate board substrate and UV-cured at a speed of 5 m / s under a UV lamp at 120°C to form a 0.15 mm negative oxygen ion antibacterial layer on the surface of the calcium silicate board substrate, thus obtaining the negative oxygen ion antibacterial board.

[0093] Example 2

[0094] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 2.

[0095] Example 3

[0096] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 3.

[0097] Example 4

[0098] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 4.

[0099] Example 5

[0100] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 5.

[0101] Example 6

[0102] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 6.

[0103] Example 7

[0104] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 7.

[0105] Example 8

[0106] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 8.

[0107] Example 9

[0108] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 9.

[0109] Example 10

[0110] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 10.

[0111] Example 11

[0112] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 11.

[0113] Example 12

[0114] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 12.

[0115] Example 13

[0116] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 13.

[0117] Example 14

[0118] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 14.

[0119] Example 15

[0120] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 15.

[0121] Example 16

[0122] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive is the same as that used in Preparation Example 16.

[0123] Example 17

[0124] A negative oxygen ion antibacterial board and its preparation method are as follows:

[0125] After mixing 30 parts of UV-curable resin, 35 parts of HDDA monomer, 2.5 parts of photoinitiator, 0.3 parts of leveling and wetting agent, 0.5 parts of antifoaming agent, and 10 parts of the functional adhesive prepared in Preparation Example 17, the mixture was applied to the surface of a calcium silicate board substrate and UV-cured at 5 m / s under a 120°C UV lamp to form a 0.15 mm negative ion antibacterial layer on the surface of the calcium silicate board substrate, thus obtaining a negative ion antibacterial board.

[0126] Example 18

[0127] A negative oxygen ion antibacterial board and its preparation method are as follows:

[0128] After mixing 45 parts of UV-curable resin, 50 parts of HDDA monomer, 3.5 parts of photoinitiator, 0.5 parts of leveling and wetting agent, 0.6 parts of antifoaming agent, and 15 parts of the functional adhesive prepared in Preparation Example 16, the mixture was applied to the surface of the magnesium oxide board substrate and UV-cured at 5 m / s under a UV lamp at 120°C to form a 0.15 mm negative oxygen ion antibacterial layer on the surface of the magnesium oxide board substrate, thus obtaining a negative oxygen ion antibacterial board.

[0129] Comparative Example 1

[0130] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain hydroxypropyltrimethylammonium chloride chitosan.

[0131] Comparative Example 2

[0132] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that: the functional adhesive in Preparation Example 1 does not contain inorganic antibacterial agents, and the negative oxygen ion mineral powder is 24.5 parts, which consists of 4.9 parts of 1~5μm zeolite micron powder, 11.43 parts of tourmaline submicron powder, 2.45 parts of purple jade submicron powder and 5.72 parts of red ochre submicron powder.

[0133] Comparative Example 3

[0134] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain nano-silver and 7 parts of nano-zinc oxide.

[0135] Comparative Example 4

[0136] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain nano zinc oxide or 7 parts of nano silver.

[0137] Comparative Example 5

[0138] A negative ion antibacterial board and its preparation method differ from Example 1 in that: the functional adhesive in Example 1 does not contain 1-5 μm zeolite micron powder, and the negative ion mineral powder consists of 10.17 parts tourmaline submicron powder, 2.75 parts purple jade submicron powder, and 4.58 parts red ochre submicron powder.

[0139] Comparative Example 6

[0140] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain purple jade submicron powder, and the negative oxygen ion mineral powder consists of 3.5 parts of 1~5μm zeolite micron powder, 9.17 parts of tourmaline submicron powder and 4.83 parts of red ochre submicron powder.

[0141] Comparative Example 7

[0142] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that: the functional adhesive in Example 1 does not contain red ochre submicron powder, and the negative oxygen ion mineral powder consists of 4.5 parts of 1~5μm zeolite micron powder, 11.25 parts of tourmaline submicron powder and 2.75 parts of purple jade submicron powder.

[0143] Comparative Example 8

[0144] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain tourmaline submicron powder, and the negative oxygen ion mineral powder consists of 6.5 parts of 1~5μm zeolite micron powder, 3.75 parts of purple jade submicron powder and 7.25 parts of red ochre submicron powder.

[0145] Comparative Example 9

[0146] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain sodium polyacrylate.

[0147] Comparative Example 10

[0148] A negative oxygen ion antibacterial board and its preparation method differ from Example 1 in that the functional adhesive in Example 1 does not contain dodecylphenol polyoxyethylene ether.

[0149] Comparative Example 11

[0150] A negative ion antibacterial board and its preparation method differ from Example 1 in that: a functional active agent replaces the functional adhesive of Example 1. The functional active agent is prepared by mixing 0.36 parts of sodium polyacrylate, 0.18 parts of dodecylphenol polyoxyethylene ether, 2.93 parts of negative ion antibacterial composite powder, 0.78 parts of hydroxypropyltrimethylammonium chloride chitosan, and 0.48 parts of silane coupling agent KH550 evenly to obtain the functional active agent, which does not contain polyurethane modified acrylate adhesive.

[0151] Comparative Example 12

[0152] A negative oxygen ion antibacterial board and its preparation method differ from Example 11 in that: in step (3), the wet gel is dried in an oven at 60~65℃ under normal pressure for 10h to form a dry gel, and then the dry gel is initially ground to a particle size greater than 200 mesh, and then the temperature is gradually increased to 495℃ at a rate of 5~6℃ / min for sintering and holding for 2h. After natural cooling, it is ground to a particle size of 0.1~2μm to obtain an inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, namely negative oxygen ion antibacterial composite powder.

[0153] Performance testing

[0154] The negative oxygen ion antibacterial plates obtained in Examples 1-18 and the negative oxygen ion antibacterial plates obtained in Comparative Examples 1-11 were used as samples for performance testing.

[0155] 1) Indoor air negative ion concentration test: Refer to JC / T 2110-2012 "Indoor Air Ion Concentration Test Method", chamber volume 1m³ 3 The concentration of negative air ions was obtained after the chamber was sealed for 2 hours. (Negative air ion concentration (ions / m³)) 3As shown in Table 1.

[0156] 2) Radioactivity test: Refer to GB 6566-2010 "Limits of Radionuclides in Building Materials", and the results are shown in Table 1.

[0157] 3) Antiviral activity test: Referring to ISO 21702:2019 "Determination of antiviral activity of plastics and other non-porous surfaces", the samples were treated at room temperature for 18h and 24h to determine the antiviral activity against influenza A virus H3N2 and influenza A virus H1N1. The antiviral activity rate (%) is shown in Table 1.

[0158] 4) Antibacterial performance test: Referring to JIS Z 2810:2010 (COR1:2011, AMD 1:2012) "Test for antibacterial activity and efficacy of antibacterial products", the antibacterial rate (%) of Escherichia coli and Staphylococcus aureus after 18h and 24h of treatment at room temperature is shown in Table 1.

[0159] 5) Anti-mildew performance test: Refer to GB / T 24128-2009 "Test Method for Anti-mildew Performance of Plastics". The mold grade and coverage (%) are shown in Table 1. The evaluation criteria are as follows: Grade 0: No mold growth visible to the naked eye, and mycelial coverage under a microscope <10%; Grade 1: Mold coverage area ≤25%; Grade 2: Mold coverage area 26%~50%; Grade 3: Mold coverage area 51%~75%; Grade 4: Mold coverage area >75%; The final anti-mildew grade is based on the most severely affected area on the sample surface.

[0160] 6) Adhesion performance test: Refer to ISO 2409:2020 "Paints and varnishes - Cross-cut test", the adhesion grades are shown in Table 1; where the evaluation criteria are: Grade 0: The cut edge is completely smooth and there is no peeling; Grade 1: Small pieces peel off at the intersection of the cuts, and the actual damage is ≤5%; Grade 2: Peeling area is 5%~15%; Grade 3: Peeling area is 15%~35%; Grade 4: Peeling area is 35%~65%; Grade 5: Peeling area is >65%.

[0161] Table 1 Performance Testing

[0162]

[0163] Stability test

[0164] Test on the change in the initial release of negative oxygen ions under high temperature and high humidity: The negative oxygen ion antibacterial boards obtained in Examples 1-18 and Comparative Examples 1-11 were subjected to an environment with a temperature of 30℃, relative humidity of 50%, and light intensity of 10000 Lux for 1 hour. The concentration of negative oxygen ions was recorded as S1. In the same way, with other conditions unchanged, the concentration of negative oxygen ions was recorded as S2 at a temperature of 60℃ and relative humidity of 95%. The change rate of the initial release of negative oxygen ions was calculated as change rate (%) = (S2-S1) / S1. The results are shown in Table 2. The higher the change rate, the greater the influence of temperature on the release of negative oxygen ions, resulting in a larger difference in the release of negative oxygen ions before and after. The stability of the negative oxygen ion release efficiency of the negative oxygen ion antibacterial layer is poor, which in turn affects the durability of the negative oxygen ion antibacterial layer in antibacterial and antiviral properties.

[0165] Table 2 Stability Test

[0166]

[0167] Based on Tables 1 and 2 above, the negative ion antibacterial board of the present invention is provided with a negative ion antibacterial layer. A comparison of Examples 1-3 with Comparative Examples 1-11 reveals that the functional adhesive used in the negative ion antibacterial layer, comprising polyurethane-modified acrylate adhesive, negative ion antibacterial composite powder, and chitosan quaternary ammonium salt, not only enhances the stability of the functional adhesive in the negative ion antibacterial layer, giving the negative ion antibacterial layer excellent adhesion to the board substrate and improving its antibacterial, antiviral, and antifungal effects, but also improves its antibacterial, antiviral, and antifungal durability. The addition of sodium polyacrylate and... Dialkylphenol polyoxyethylene ether improves the uniformity of the dispersion of negative ion antibacterial composite powder and chitosan quaternary ammonium salt in the functional adhesive, while also enhancing the stability of the negative ion release efficiency of the negative ion antibacterial layer. Moreover, the zinc oxide and silver in the negative ion antibacterial composite powder synergistically enhance the antibacterial and mold-purifying effects with the chitosan quaternary ammonium salt. In addition, the negative ion mineral powder, composed of zeolite micron powder, tourmaline submicron powder, purple jade submicron powder, and red ochre submicron powder, works synergistically to effectively improve the stability of negative ion release efficiency and increase the concentration of negative ions, resulting in good antibacterial, antiviral, and anti-mold effects.

[0168] Compared with Examples 7 and 11, in the functional adhesive, the chitosan quaternary ammonium salt coating the surface of the negative ion antibacterial composite powder is more conducive to improving the stability of negative ion release efficiency and the concentration of negative ions, thereby improving the durability of the negative ion antibacterial layer and having better antibacterial, antiviral and antifungal effects. Moreover, compared with Example 11, Example 7 found that the negative ion antibacterial composite powder is an inorganic antibacterial agent-negative ion mineral powder supported composite powder, which can further improve the concentration of negative ions and the stability of negative ion release efficiency in the negative ion antibacterial layer. At the same time, the antibacterial, antiviral and antifungal properties are further improved, and it has excellent antibacterial and purification synergistic performance.

[0169] Compared with Examples 1-6, Examples 7-8-10, Examples 11-13, and Examples 12-14-16, the negative oxygen ion mineral powder in the negative oxygen ion antibacterial composite powder, after calcination and / or plasma pretreatment, significantly enhances the activity of the negative oxygen ion antibacterial composite powder. This results in a higher concentration of negative oxygen ions in the negative oxygen ion antibacterial layer and better stability of negative oxygen ion release efficiency. Simultaneously, it improves antibacterial, antiviral, and antifungal properties, giving the negative oxygen ion antibacterial layer better durability and achieving superior antibacterial and purification synergy. Furthermore, compared with Examples 11 and 13, and Examples 16, the use of supercritical drying further enhances the effect of the inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder.

[0170] In summary, the negative ion antibacterial board of the present invention uses a functional adhesive in the negative ion antibacterial layer to generate a high concentration of negative ions, thereby achieving antibacterial, antiviral and anti-mildew effects.

[0171] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit and essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0172] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A negative ion antibacterial board, characterized in that, The material includes a substrate and a negative ion antibacterial layer. The negative ion antibacterial layer is prepared from raw materials comprising the following parts by weight: 30-45 parts of photocurable resin, 35-50 parts of HDDA monomer, 2.5-3.5 parts of photoinitiator, 0.3-0.5 parts of leveling and wetting agent, 0.5-0.6 parts of antifoaming agent, and 10-15 parts of functional adhesive. The functional adhesive is prepared from the following raw materials in parts by weight: 60-70 parts of polyurethane modified acrylate adhesive, 20-30 parts of negative oxygen ion antibacterial composite powder, 5-8 parts of chitosan quaternary ammonium salt, 2-4 parts of sodium polyacrylate, 0-0.04 parts of sodium polyphosphate, 1-2 parts of dodecylphenol polyoxyethylene ether, and 3-5 parts of silane coupling agent. The preparation method of the functional adhesive is as follows: (1) Chitosan quaternary ammonium salt is dissolved in an ethanol aqueous solution with pH 6~7 to form a 1.5~2% chitosan quaternary ammonium salt solution. Then, dodecylphenol polyoxyethylene ether and negative oxygen ion antibacterial composite powder are added and stirred to disperse evenly to form a uniform suspension. Then, sodium polyphosphate is added and stirred evenly. The temperature is raised to 60~65℃ and stirred for 2~3 hours. The mixture is then filtered and dried to obtain negative oxygen ion antibacterial composite powder coated with chitosan quaternary ammonium salt. (2) Add sodium polyacrylate to polyurethane modified acrylate adhesive, stir until completely dissolved, then add dodecylphenol polyoxyethylene ether and mix evenly to obtain a uniform base liquid. (3) Mix the chitosan quaternary ammonium salt-coated negative oxygen ion antibacterial composite powder with silane coupling agent and stir evenly, then add it to the uniform base liquid and stir to disperse evenly to obtain a functional adhesive. The negative oxygen ion antibacterial composite powder is an inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder. The inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder is prepared from negative oxygen ion mineral powder, zinc nitrate, silver nitrate, ethanol aqueous solution, citric acid, and ammonia water as raw materials through sol-gel method, drying, initial grinding, sintering, and grinding. The negative oxygen ion mineral powder is composed of zeolite micron powder, tourmaline submicron powder, purple jade submicron powder, and red ochre submicron powder; the inorganic antibacterial agent is composed of zinc oxide and silver.

2. The negative ion antibacterial board according to claim 1, characterized in that, In the negative oxygen ion antibacterial composite powder, the negative oxygen ion mineral powder is pretreated by calcination and / or plasma technology.

3. The negative ion antibacterial board according to claim 1, characterized in that, The mass ratio of the zeolite micron powder, tourmaline submicron powder, purple jade submicron powder and red ochre submicron powder is 3:6~8:1~2:3~4; The mass ratio of zinc oxide to silver is 8~10:

1.

4. The negative ion antibacterial board according to claim 2, characterized in that, The particle size of the inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder is 0.1~2μm.

5. The negative ion antibacterial board according to claim 1, characterized in that, In the preparation of inorganic antibacterial agent-negative oxygen ion mineral powder supported composite powder, the sintering conditions are to gradually increase the temperature to 470~500℃ at a rate of 1~2℃ / min and then hold it at that temperature for sintering.

6. The negative ion antibacterial board according to claim 1, characterized in that, The preparation method of the negative ion antibacterial board is as follows: After uniformly mixing the light-curing resin, HDDA monomer, photoinitiator, leveling and wetting agent, defoaming agent and functional adhesive, the mixture is coated onto the surface of the board substrate. After UV curing, a negative ion antibacterial layer is formed on the surface of the board substrate, thus obtaining the negative ion antibacterial board. The substrate of the board is either calcium silicate board or magnesium oxide board.

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