Antiviral water paint for interior wall and preparation method thereof

Abstract

The application discloses an antiviral water paint for interior walls and a preparation method thereof, and belongs to the technical field of water-based paint materials. The application is used to solve the technical problem that the antiviral and antibacterial performance and the moisture resistance of the antiviral paint in the prior art need to be further improved. The antiviral water paint for interior walls comprises the following components in parts by weight: 90-105 parts of an antibacterial and antiviral emulsion, 1.0-1.3 parts of a dispersing agent, 0.5-0.8 parts of a wetting agent, 0.6-1.0 parts of a defoaming agent, 1.2-1.5 parts of a thickening agent and 20-25 parts of an activated filler. In the polysiloxane silicone emulsion containing polyolefin, the antibacterial agent, modified zinc oxide and acrylic monomer are prepared into the antibacterial and antiviral emulsion in a free radical polymerization mode, and the activated filler is cooperated with each other, so that the storage stability of the water-based paint is effectively improved, and the moisture resistance, scrub resistance, long-acting antibacterial and antiviral performance of the paint film of the water-based paint are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based paint, in particular to an anti-virus water paint for interior walls and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards and the enhancement of health awareness, the health and safety of indoor environment are increasingly required, and interior wall coating as an important material for indoor decoration directly affects the health and quality of life of the occupants. Although traditional interior wall coating can meet the basic decoration and protection functions, it has obvious shortcomings in terms of anti-virus and antibacterial properties, and cannot effectively resist the spread of viruses and bacteria, which poses a potential threat to people's health. In order to meet this challenge, some interior wall coatings with antibacterial and antiviral functions have appeared in the market.

[0003] A water-based anti-virus varnish and a preparation method thereof are disclosed in a Chinese patent application with publication number CN115386288A, which belongs to the technical field of varnish. The water-based anti-virus varnish includes a water-based polyurethane emulsion and a composite anti-virus agent. The composite anti-virus agent includes nano-silver, nano-silicon dioxide, a reducing agent, an amino acid, a potassium salt, and alkyl dimethyl benzyl ammonium chloride. The water-based anti-virus varnish has excellent anti-virus function by adding a composite anti-virus agent with anti-virus effect. It not only has high anti-virus rate and good broad-spectrum antibacterial property, but also has good high-temperature resistance and weather resistance due to its main inorganic components, and is non-irritating and more environmentally friendly. At the same time, the composite anti-virus agent uses nano-silicon dioxide as a carrier, and adds amino acid stabilizers and potassium salts to avoid poor dispersion and stability of nano-silver due to agglomeration, and improve anti-virus property.

[0004] However, the anti-virus performance of existing antibacterial water-based paint is mainly based on silver ions as the main anti-virus component. Other materials such as zinc oxide, although have anti-virus performance, have limited anti-virus performance and are difficult to meet the antibacterial and anti-virus requirements of antibacterial coatings. In addition, the existing anti-virus paint mostly adds inorganic fillers as fillers, but the inorganic fillers are prone to sedimentation and caking in the paint, and the antibacterial and antiviral coatings are in contact with water or cleaning solution, and water quickly penetrates, which easily causes phenomena such as scrubbing and peeling, resulting in the need for further improvement of the moisture and scrubbing resistance of the antibacterial paint.

[0005] In view of the above technical defects, a solution is proposed. SUMMARY

[0006] The application aims to provide an anti-virus water paint for interior walls and a preparation method thereof, and aims to solve the technical problem that the antibacterial performance, storage stability and wet and scrubbing resistance of the anti-virus paint in the prior art need to be further improved.

[0007] The application aims to provide an anti-virus water paint for interior walls and a preparation method thereof, and aims to solve the technical problem that the antibacterial performance, storage stability and wet and scrubbing resistance of the anti-virus paint in the prior art need to be further improved.

[0008] An anti-virus water paint for interior walls comprises the following components in parts by weight: 90-105 parts of an antibacterial and anti-virus emulsion, 1.0-1.3 parts of a dispersing agent, 0.5-0.8 parts of a wetting agent, 0.6-1.0 parts of an antifoaming agent, 1.2-1.5 parts of a thickening agent and 20-25 parts of an activated filler.

[0009] The preparation method of the antibacterial and anti-virus emulsion is as follows: hydroxypropyl acrylate, butyl acrylate, acrylic acid, an antibacterial agent, modified zinc oxide and a silicon microemulsion are added to a three-necked flask, and are rapidly stirred for 30-50 min, the temperature of the three-necked flask is increased to 75-85 DEG C, an initiator solution is added dropwise into the three-necked flask, and the reaction is carried out for 4-6 h, and the antibacterial and anti-virus emulsion is obtained after post-treatment.

[0010] The reaction formula for synthesizing the antibacterial and anti-virus emulsion is as follows:

[0011]

[0012] In the formula, R is a C1-C4 alkyl group, and n is 1-3.

[0013]

[0014] The modified zinc oxide is as follows:

[0015] The reaction mechanism for synthesizing the antibacterial and anti-virus emulsion is as follows:

[0016] In the reaction process, the hydroxypropyl acrylate, butyl acrylate, acrylic acid, antibacterial agent and modified zinc oxide are uniformly dispersed in the emulsion, and the unsaturated olefin double bonds on the molecules are subjected to free radical polymerization reaction under the action of the initiator, so that a polyolefin long chain with multiple branched chains is generated, and after the reaction is completed, the pH of the reaction system is adjusted by using ammonia water, the carboxylic acid groups are subjected to acid-base neutralization with the ammonia water, so that the carboxylic acid ammonium salt is formed, and the antibacterial and anti-virus emulsion is prepared.

[0017] Further, the dispersing agent is polyethylene glycol 400, the wetting agent is sodium butylnaphthalene sulfonate, the defoaming agent is defoaming agent GP-330, and the thickening agent is thickening agent SN-612; the use amount ratio of the hydroxypropyl acrylate, butyl acrylate, acrylic acid, antibacterial agent, modified zinc oxide, silicon microemulsion, and initiator solution is 7-8 g:3-4 g:2-3 g:4-5 g:1.6-2.3 g:50-60 mL:2 g, the initiator solution is composed of potassium persulfate and deionized water in a weight ratio of 1:5, the stirring speed is 800-1000 r / min, and the post-treatment comprises: after the reaction is completed, 3-5 mol / L ammonia water is added dropwise into the three-necked flask, the pH of the system is adjusted to 8-8.5, the temperature of the three-necked flask is reduced to room temperature, and the product is filtered through a 200-mesh screen to obtain the antibacterial and antiviral emulsion.

[0018] Further, the preparation method of the antibacterial agent comprises: adding diethylaminoethyl methacrylate and 1-bromo octane into a three-necked flask and stirring, and reacting at room temperature for 12-14 h, and then post-treating to obtain the antibacterial agent.

[0019] The synthesis reaction formula of the antibacterial agent is:

[0020]

[0021] The synthesis reaction mechanism of the antibacterial agent is:

[0022] During the reaction, the tertiary amine group on the diethylaminoethyl methacrylate molecule acts as a nucleophile to attack the bromine atom in 1-bromo octane, after the bromine atom is removed, a new covalent bond is formed between the oxygen atom of the diethylaminoethyl methacrylate and the carbon atom of 1-bromo octane, to generate a positively charged intermediate and a negatively charged bromide ion, thereby forming the antibacterial agent product, and the hydrogen spectrum data of the antibacterial agent is: 1H-NMR (600 MHz; CDCl3; ppm): 1.01 (3H), 1.43 (2H), 1.77 (3H), 1.96 (3H), 3.51 (6H), 3.66 (2H), 4.18 (2H), 4.67 (2H), 5.70 (1H), 6.16 (1H).

[0023] Further, the weight ratio of the diethylaminoethyl methacrylate and 1-bromo octane is 2:3, and the post-treatment comprises: after the reaction is completed, n-hexane is added into the three-necked flask, the mixture is stirred and heated for 2-3 h, then filtered, the filter cake is washed with n-hexane for 3 times and then dried, the filter cake is transferred into a drying box with a temperature of 50-60℃, and vacuum dried to constant weight to obtain the antibacterial agent.

[0024] Further, the preparation method of the modified zinc oxide is as follows: the nano zinc oxide, anhydrous ethanol and sorbic acid are added into a three-necked flask, ultrasonic dispersion is performed for 30-50 min, then stirring is performed, the temperature of the three-necked flask is increased to 60-65 DEG C, and the reaction is performed for 10-12 h, and the modified zinc oxide is obtained after post-treatment.

[0025] The synthesis reaction mechanism of the modified zinc oxide is as follows:

[0026] The hydroxyl group on the surface of the nano zinc oxide has weak alkalinity, and the acid-base neutralization reaction occurs with the carboxyl group of the sorbic acid, so that the ionic bond is formed between the nano zinc oxide and the sorbic acid, and the oxygen atom of the carboxyl group in the sorbic acid molecule provides a lone pair of electrons which can be combined with the zinc ion through coordination reaction to form a coordination bond, so that the sorbic acid is adsorbed on the surface of the nano zinc oxide, the surface of the nano zinc oxide is modified, and the modified zinc oxide is prepared.

[0027] Further, the use amount ratio of the nano zinc oxide, the anhydrous ethanol and the sorbic acid is 10 g:100 mL:0.8-1.2 g, the particle size of the nano zinc oxide is 10-20 μm, and the post-treatment includes the following steps: after the reaction is completed, the temperature of the three-necked flask is reduced to room temperature, filtration is performed, the filter cake is washed with the anhydrous ethanol for three times, then the filter cake is dried, the filter cake is transferred into a drying box with a temperature of 50-60 DEG C, and vacuum drying is performed until the constant weight is obtained, so that the modified zinc oxide is obtained.

[0028] Further, the preparation method of the silicon microemulsion is as follows: the methyl vinyl diethoxysilane, octamethylcyclotetrasiloxane and emulsion are added into a three-necked flask, rapid stirring and dispersion are performed for 20-30 min, the temperature of the three-necked flask is increased to 70-80 DEG C, the catalyst is added into the three-necked flask, and the stirring and heat preservation are performed for 60-80 min, so that the silicon microemulsion is obtained.

[0029] The synthesis reaction formula of the silicon microemulsion is as follows:

[0030]

[0031] The synthesis reaction mechanism of the silicon microemulsion is as follows:

[0032] The methyl vinyl diethoxysilane, octamethylcyclotetrasiloxane and emulsion are mixed and uniformly dispersed through stirring, under the high-temperature environment, the addition of the dodecylbenzenesulfonic acid promotes the hydrolysis and polycondensation reaction of the silicon source, and the stable silicon microemulsion with the unsaturated double bond modified polysiloxane segment is gradually formed.

[0033] Further, the methyl vinyl diethoxysilane, octamethylcyclotetrasiloxane, emulsion and catalyst are in a ratio of 2g:5g:50-60mL:0.5g, the catalyst is dodecyl benzene sulfonic acid, the emulsion is composed of sodium dodecyl sulfate, OP-10, Tween-80 and deionized water in a ratio of 3g:1g:1g:100mL, and the stirring speed is 800-1000r / min.

[0034] Further, the activated filler is obtained by the following steps:

[0035] A1, the filler and inorganic pigment are added into a ball mill, and after ball milling, the mixture is passed through an 800-mesh screen to obtain a mixed filler;

[0036] A2, the mixed filler, anhydrous ethanol and KH-560 are added into a three-necked flask for ultrasonic dispersion for 30-50min, and stirring is performed, the temperature of the three-necked flask is increased to 55-65℃, a catalyst solution is added into the three-necked flask, and reaction is performed for 40-60min, and then the activated filler is obtained by post-treatment.

[0037] Further, in step A1, the weight ratio of the filler to the pigment is 6-8:1, the filler is composed of kaolin and talcum powder in a ratio of 3:1, and the pigment is an inorganic pigment; in step A2, the ratio of the mixed filler, anhydrous ethanol, KH-560 and the catalyst solution is 5g:50mL:2g:7mL, the catalyst solution is a 0.1-0.3mol / L sodium hydroxide solution, and the post-treatment includes: after the reaction is completed, the temperature of the three-necked flask is reduced to room temperature, filtration is performed, the filter cake is washed with purified water for 3 times and then is dried, the filter cake is transferred into a drying box with a temperature of 70-80℃, and vacuum drying is performed until the weight is constant to obtain the activated filler.

[0038] A preparation method of an anti-virus water paint for interior walls, comprising the following steps:

[0039] S1, according to the formula amount, an antibacterial and antiviral emulsion is added into a three-necked flask for stirring, a dispersing agent, a wetting agent, a defoaming agent, a thickening agent and an activated filler are sequentially added into the three-necked flask, and stirring is performed for 30-50min to obtain a water-based paint crude product;

[0040] S2, the water-based paint crude product is transferred into a sand mill, and high-speed sanding is performed to obtain a water-based paint with a fineness of 20-25μm.

[0041] The present application has the following advantages:

[0042] 1. The antiviral water paint for interior walls of the present application, by synthesizing a quaternary ammonium salt antibacterial agent, and in the environment of silica emulsion, using polysiloxane containing polyolefin in silica emulsion as crosslinking agent, combining the antibacterial agent with modified zinc oxide and acrylic monomer to form a polyolefin antibacterial and antiviral emulsion with a large number of hydrophilic groups, by adjusting the pH of the system, converting the carboxyl groups in the polyolefin antibacterial and antiviral emulsion molecules into carboxylate, further improving the dispersion stability of the emulsion, so that the antibacterial and antiviral emulsion can maintain good storage stability, the brominated quaternary ammonium salt structure of the antibacterial agent combines with the negative charge of the bacterial cell membrane through the cationic charge, destroys the integrity of the bacterial cell membrane, causes the bacterial content to flow out and die, at the same time, the modification of long alkane chain enhances its penetration ability and stability on the bacterial cell membrane, zinc oxide destroys the structure and function of bacterial cell membrane by releasing zinc ions, the modification of nano zinc oxide by sorbic acid makes the antibacterial performance of nano zinc oxide persistent, the antibacterial agent cooperates with modified zinc oxide to improve the antibacterial and antiviral performance of water-based paint.

[0043] 2. The antiviral water paint for interior walls of the present application, by introducing polyolefin modified polysiloxane chain into the polyolefin segment in the antibacterial and antiviral emulsion, increasing the crosslinking degree of polyolefin molecules, forming crosslinked structure, improving the physical and chemical stability of the paint, the waterproof performance of polysiloxane makes it can significantly improve the waterproof performance of paint film when used as crosslinking agent, at the same time, due to the softness and elasticity of polysiloxane, the paint film is not easy to break or fall off when being scrubbed, improving the wet and scrubbing resistance of paint film; by surface modification of mixed filler with KH-560, the activated filler can be uniformly dispersed in the antibacterial and antiviral emulsion, improving the dispersibility of activated filler in the antibacterial and antiviral emulsion, preventing the filler from settling and agglomerating during storage, improving the storage stability of paint, the quaternary ammonium salt molecules in the emulsion can catalyze the ring opening condensation of epoxy group and hydroxyl group or other active groups on the polyolefin molecular chain at room temperature, improving the crosslinking degree of paint film layer, further improving the wet and scrubbing resistance of paint film. DETAILED DESCRIPTION

[0044] The technical solutions of the present application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0045] Embodiment 1

[0046] The present embodiment provides a preparation method of an antiviral water paint for interior walls, comprising the following steps:

[0047] S1, preparation of antibacterial agent

[0048] Weigh: diethylaminoethyl methacrylate 20 g, 1-bromooctane 30 g is added to a three-necked flask, stirring, room temperature reaction for 12 h, add n-hexane 100 mL to the three-necked flask, stirring for 2 h, suction filtration, the filter cake is washed with n-hexane for 3 times and then suctioned dry, the filter cake is transferred to a drying box with a temperature of 50 DEG C, vacuum dried to constant weight, to obtain an antibacterial agent.

[0049] S2, preparation of modified zinc oxide

[0050] Weigh: nano zinc oxide with a particle size of 10-20 μm 50 g, anhydrous ethanol 500 mL and sorbic acid 4 g are added to a three-necked flask, ultrasonic dispersion for 30 min and then stirring, the temperature of the three-necked flask is increased to 60 DEG C, and the reaction is kept for 10 h, the temperature of the three-necked flask is reduced to room temperature, suction filtration, the filter cake is washed with anhydrous ethanol for 3 times and then suctioned dry, the filter cake is transferred to a drying box with a temperature of 50 DEG C, vacuum dried to constant weight, to obtain modified zinc oxide.

[0051] S3, preparation of silicon microemulsion

[0052] Sodium dodecyl sulfate, OP-10, Tween-80 and deionized water are added to a beaker in a ratio of 3 g:1 g:1 g:100 mL, and stirred uniformly to obtain an emulsion;

[0053] Weigh: methylvinyl diethoxysilane 20 g, octamethylcyclotetrasiloxane 50 g and emulsion 500 mL are added to a three-necked flask, the stirring speed is set to 800 r / min, stirring and dispersing for 20 min, the temperature of the three-necked flask is increased to 70 DEG C, dodecylbenzenesulfonic acid 5 g is added to the three-necked flask, and stirring is kept for 60 min to obtain a silicon microemulsion.

[0054] S4, preparation of antibacterial and antiviral emulsion

[0055] Potassium persulfate and deionized water are mixed uniformly in a weight ratio of 1:5 to obtain an initiator solution;

[0056] Weigh: hydroxypropyl acrylate 70 g, butyl acrylate 30 g, acrylic acid 20 g, antibacterial agent 40 g, modified zinc oxide 16 g and silicon microemulsion 500 mL are added to a three-necked flask, the stirring speed is set to 800 r / min, stirring for 30 min, the temperature of the three-necked flask is increased to 75 DEG C, the initiator solution 20 g is added dropwise to the three-necked flask, and the reaction is kept for 4 h, 3 mol / L ammonia water is added dropwise to the three-necked flask to adjust the pH of the system to 8, the temperature of the three-necked flask is reduced to room temperature, and it is passed through a 200 mesh screen to obtain an antibacterial and antiviral emulsion.

[0057] S5, preparation of activated filler

[0058] Mix kaolin and talcum powder in a weight ratio of 3:1 to obtain the filler;

[0059] Add the filler and green iron oxide into a ball mill in a weight ratio of 6:1, sieve through an 800-mesh screen after ball milling, and obtain the mixed filler;

[0060] Weigh: add 50 g of the mixed filler, 500 mL of anhydrous ethanol, and 20 g of KH-560 into a three-necked flask, ultrasonic dispersion for 30 min, stirring, and increase the temperature of the three-necked flask to 55°C; add 70 mL of 0.1 mol / L sodium hydroxide solution into the three-necked flask, and keep the temperature for 40 min; reduce the temperature of the three-necked flask to room temperature, filter, wash the filter cake with purified water for 3 times, and then dry; transfer the filter cake to a drying oven with a temperature of 70°C, and vacuum dry until the weight is constant to obtain the activated filler.

[0061] S6, preparation of water-based paint

[0062] Weigh by weight: add 90 parts of the antibacterial and antiviral emulsion into a three-necked flask and stir; add 1.0 part of polyethylene glycol 400, 0.5 part of sodium butylnaphthalene sulfonate, 0.6 part of defoamer GP-330, 1.2 parts of thickening agent SN-612, and 20 parts of the activated filler into the three-necked flask in sequence; stir for 30 min, and transfer it to a sand mill for high-speed sanding to obtain water-based paint with a fineness of 20-25 μm, which is stored in an environment below 15°C.

[0063] Example 2

[0064] The present embodiment provides a preparation method of an antiviral water paint for interior walls, which comprises the following steps:

[0065] S1, preparation of an antibacterial agent

[0066] Weigh: add 20 g of diethylaminoethyl methacrylate and 30 g of 1-bromo octane into a three-necked flask and stir; react at room temperature for 13 h; add 100 mL of n-hexane into the three-necked flask, and keep stirring for 2.5 h; filter, wash the filter cake with n-hexane for 3 times, and then dry; transfer the filter cake to a drying oven with a temperature of 55°C, and vacuum dry until the weight is constant to obtain the antibacterial agent.

[0067] S2, preparation of modified zinc oxide

[0068] Weigh: add 50 g of nano zinc oxide with a particle size of 10-20 μm, 500 mL of anhydrous ethanol, and 5 g of sorbic acid into a three-necked flask, ultrasonic dispersion for 40 min, and then stir; increase the temperature of the three-necked flask to 63°C, and keep the temperature for 11 h; reduce the temperature of the three-necked flask to room temperature, filter, wash the filter cake with anhydrous ethanol for 3 times, and then dry; transfer the filter cake to a drying oven with a temperature of 55°C, and vacuum dry until the weight is constant to obtain the modified zinc oxide.

[0069] S3, Preparation of silicon microemulsion

[0070] Sodium dodecyl sulfate, OP-10, Tween-80 and deionized water were added to a beaker in a ratio of 3g:1g:1g:100mL, stirred uniformly to obtain an emulsion;

[0071] Methyl vinyl diethoxysilane 20g, octamethylcyclotetrasiloxane 50g and emulsion 550mL were weighed into a three-necked flask, the stirring speed was set to 900r / min, and stirring and dispersion were carried out for 25min. The temperature of the three-necked flask was raised to 75℃, 5g of dodecylbenzenesulfonic acid was added to the three-necked flask, and the temperature was maintained and stirred for 70min to obtain a silicon microemulsion.

[0072] S4, Preparation of antibacterial and antiviral emulsion

[0073] Potassium persulfate and deionized water were mixed uniformly in a weight ratio of 1:5 to obtain an initiator solution;

[0074] Acrylate 75g, butyl acrylate 35g, acrylic acid 25g, antibacterial agent 45g, modified zinc oxide 30g and silicon microemulsion 550mL were weighed into a three-necked flask, the stirring speed was set to 900r / min, and stirring was carried out for 40min. The temperature of the three-necked flask was raised to 80℃, 20g of the initiator solution was added dropwise to the three-necked flask, and the temperature was maintained and reacted for 5h. 4mol / L ammonia water was added dropwise to the three-necked flask to adjust the pH to 8.3. The temperature of the three-necked flask was reduced to room temperature, and the mixture was passed through a 200-mesh screen to obtain an antibacterial and antiviral emulsion.

[0075] S5, Preparation of activated filler

[0076] Kaolin and talcum powder were mixed uniformly in a weight ratio of 3:1 to obtain a filler;

[0077] The filler and iron oxide orange were added to a ball mill in a weight ratio of 7:1, and after ball milling, the mixture was passed through an 800-mesh screen to obtain a mixed filler;

[0078] The mixed filler 50g, anhydrous ethanol 500mL and KH-560 20g were weighed into a three-necked flask and ultrasonically dispersed for 40min, and then stirred. The temperature of the three-necked flask was raised to 60℃, 0.2mol / L sodium hydroxide solution 70mL was added to the three-necked flask, and the temperature was maintained and reacted for 50min. The temperature of the three-necked flask was reduced to room temperature, and the mixture was suction filtered. The filter cake was washed with purified water for 3 times and then suction dried. The filter cake was transferred to a drying oven with a temperature of 75℃, and vacuum dried to constant weight to obtain an activated filler.

[0079] S6, Preparation of water-based paint

[0080] Take by weight parts: 98 parts of antibacterial and antiviral emulsion into a three-necked flask and stir, add polyethylene glycol 400 1.15 parts, sodium butylnaphthalene sulfonate 0.65 parts, defoamer GP-330 0.8 parts, thickening agent SN-612 1.35 parts and activated filler 23 parts into the three-necked flask in turn, stir for 40 min, transfer it to a sand mill, grind sand at high speed, get water-based paint with fineness of 20-25 μm, store in an environment below 20℃.

[0081] Example 3

[0082] The embodiment provides a preparation method of an antiviral water paint for interior walls, comprising the following steps:

[0083] S1, preparation of antibacterial agent

[0084] Take: diethylaminoethyl methacrylate 20 g, 1-bromooctane 30 g into a three-necked flask and stir, react at room temperature for 14 h, add n-hexane 100 mL into the three-necked flask, heat and stir for 3 h, filter, wash the filter cake with n-hexane for 3 times and then dry, transfer the filter cake to a drying box with temperature of 60℃, vacuum dry to constant weight, get the antibacterial agent.

[0085] S2, preparation of modified zinc oxide

[0086] Take: nano zinc oxide with particle size of 10-20 μm 50 g, anhydrous ethanol 500 mL and sorbic acid 6 g into a three-necked flask, ultrasonic dispersion for 50 min and then stir, heat the three-necked flask to 65℃, heat and react for 12 h, reduce the temperature of the three-necked flask to room temperature, filter, wash the filter cake with anhydrous ethanol for 3 times and then dry, transfer the filter cake to a drying box with temperature of 60℃, vacuum dry to constant weight, get the modified zinc oxide.

[0087] S3, preparation of silicon microemulsion

[0088] Add sodium dodecyl sulfate, OP-10, Tween-80 and deionized water into a beaker according to the ratio of 3 g:1 g:1 g:100 mL, stir uniformly, get emulsion;

[0089] Take: methylvinyl diethoxysilane 20 g, octamethylcyclotetrasiloxane 50 g and emulsion 600 mL into a three-necked flask, set the stirring speed to 1000 r / min, stir and disperse for 30 min, heat the three-necked flask to 80℃, add dodecylbenzenesulfonic acid 5 g into the three-necked flask, heat and stir for 80 min, get the silicon microemulsion.

[0090] S4, preparation of antibacterial and antiviral emulsion

[0091] Mix potassium persulfate and deionized water according to the weight ratio of 1:5 uniformly, get initiator solution;

[0092] Take: hydroxypropyl acrylate 80 g, butyl acrylate 40 g, acrylic acid 30 g, antimicrobial agent 50 g, modified zinc oxide 23 g and silicon microemulsion 600 mL into a three-necked flask, set the stirring speed to 1000 r / min, stir for 50 min, the temperature of the three-necked flask is raised to 85℃, add initiator solution 20 g dropwise into the three-necked flask, keep the reaction for 6 h, add 5 mol / L ammonia water into the three-necked flask, adjust the pH of the system to 8.5, reduce the temperature of the three-necked flask to room temperature, pass through a 200 mesh screen, and obtain the antibacterial and antiviral emulsion.

[0093] S5, preparation of activated filler

[0094] Mix kaolin and talcum powder in a weight ratio of 3:1 to obtain the filler;

[0095] Add the filler and iron oxide brown into the ball mill in a weight ratio of 8:1, pass through an 800 mesh screen after ball milling, and obtain the mixed filler;

[0096] Take: add the mixed filler 50 g, anhydrous ethanol 500 mL and KH-560 20 g into a three-necked flask for ultrasonic dispersion for 50 min, stir, raise the temperature of the three-necked flask to 65℃, add 0.3 mol / L sodium hydroxide solution 70 mL into the three-necked flask, keep the reaction for 60 min, reduce the temperature of the three-necked flask to room temperature, filter, wash the filter cake with purified water for 3 times, then dry, transfer the filter cake into a drying box with a temperature of 80℃, and vacuum dry to constant weight to obtain the activated filler.

[0097] S6, preparation of water-based paint

[0098] Take: add the antibacterial and antiviral emulsion 105 parts into a three-necked flask for stirring, add polyethylene glycol 400 1.3 parts, sodium butylnaphthalene sulfonate 0.8 parts, defoamer GP-330 1.0 parts, thickening agent SN-612 1.5 parts and activated filler 25 parts into the three-necked flask in sequence, stir for 50 min, transfer it into a sand mill, and grind the sand at high speed to obtain the water-based paint with a fineness of 20-25 μm, which is stored at 25℃.

[0099] Comparative Example 1

[0100] The difference between this comparative example and Example 3 is that in step S2, sorbic acid is replaced by KH-570 in equimolar amount.

[0101] Comparative Example 2

[0102] The difference between this comparative example and Example 3 is that in step S3, no methyl vinyl diethoxysilane is added.

[0103] Comparative Example 3

[0104] The difference between the present comparative example and Example 3 is that no modified zinc oxide is added in step S4.

[0105] Comparative Example 4

[0106] The difference between the present comparative example and Example 3 is that the mixed filler in step S5 is used to replace the activated filler in step S6.

[0107] Performance test:

[0108] The antibacterial performance, antibacterial durability, and antibacterial performance after water scrubbing for 200 times of the water-based paint samples prepared in Examples 1-3 and Comparative Examples 1-4 were determined according to the standard GB / T 21866-2008 “Determination of Antibacterial Property of Antibacterial Coatings (Paint Film) and Antibacterial Effect”;

[0109] The antiviral performance of the water-based paint samples prepared in Examples 1-3 and Comparative Examples 1-4 against influenza A virus (H3N2) and enterovirus (EV71) was determined according to the standard T / CNCIA 03002-2020 “Test Method for Antiviral Performance of Coatings (Paint Film) ”;

[0110] The scrubbing resistance of the water-based paint samples prepared in Examples 1-3 and Comparative Examples 1-4 was determined according to the standard GB / T 31410-2015 “Evaluation of Wet Scrubbing Resistance and Cleanability of Color Paint and Varnish Coating”, and the wet scrubbing resistance of the paint layer was evaluated according to EN13300;

[0111] The sedimentation degree of the water-based paint samples prepared in Examples 1-3 and Comparative Examples 1-4 was evaluated according to the standard GB / T 6753.3-1986 “Test Method for Storage Stability of Coatings”;

[0112] The specific test results are shown in Table 1 below.

[0113] Table 1 - Performance test data table of samples

[0114]

[0115]

[0116] Data analysis:

[0117] Comparative analysis of the data in the above table, the water-based paint prepared by the application has a wet and scrubbing resistance grade of 1, a sedimentation degree grade of 10, excellent antibacterial performance and durability against E. coli and S. aureus, excellent antiviral performance and durability against influenza A virus and enterovirus, and good antibacterial performance after 200 times of water scrubbing, and all the performance parameters are better than those of the comparative examples, indicating that the polysiloxane with polyolefin in the silicone emulsion as the crosslinking agent, the combination of the free radical polymerization antibacterial agent and the modified zinc oxide and acrylic monomer, and the cooperation of the antibacterial and antiviral emulsion with the activated filler not only effectively improve the storage stability of the water-based paint, but also improve the wet and scrubbing resistance of the paint film and the long-acting antibacterial and antiviral performance.

[0118] The above is only an example and description of the structure of the application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the structure of the application or exceed the scope defined by the claims, which shall belong to the protection scope of the application.

[0119] In the description of the present specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0120] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present specification. The present specification selects and describes these embodiments in order to better explain the principles and practical application of the application, so that those skilled in the art can well understand and utilize the application. The application is limited only by the claims and their entire scope and equivalents.

Claims

1. An antiviral water-based paint for interior walls, characterized in that, It comprises the following components by weight: 90-105 parts antibacterial and antiviral emulsion, 1.0-1.3 parts dispersant, 0.5-0.8 parts wetting agent, 0.6-1.0 parts defoamer, 1.2-1.5 parts thickener, and 20-25 parts activated filler; The preparation method of the antibacterial and antiviral emulsion is as follows: hydroxypropyl acrylate, butyl acrylate, acrylic acid, antibacterial agent, modified zinc oxide, and silicone microemulsion are added to a three-necked flask and stirred rapidly for 30-50 minutes. The temperature of the three-necked flask is raised to 75-85°C. An initiator solution is added dropwise to the three-necked flask, and the reaction is maintained at this temperature for 4-6 hours. 3-5 mol / L ammonia water is added dropwise to the three-necked flask to adjust the pH of the system to 8-8.

5. The temperature of the three-necked flask is lowered to room temperature, and the emulsion is passed through a 200-mesh sieve to obtain the antibacterial and antiviral emulsion. The initiator solution is composed of potassium persulfate and deionized water in a weight ratio of 1:

5. The modified zinc oxide was prepared by adsorbing sorbic acid onto the surface of nano zinc oxide. The preparation method of the silicone microemulsion is as follows: methylvinyldiethoxysilane, octamethylcyclotetrasiloxane and emulsion are added to a three-necked flask, and the mixture is rapidly stirred and dispersed for 20-30 minutes. The temperature of the three-necked flask is raised to 70-80°C, a catalyst is added to the three-necked flask, and the mixture is kept at this temperature and stirred for 60-80 minutes to obtain the silicone microemulsion. The catalyst is dodecylbenzenesulfonic acid, and the emulsion is composed of sodium dodecyl sulfate, OP-10, Tween-80 and deionized water in a ratio of 3g:1g:1g:100mL. The method for preparing the antibacterial agent is as follows: Diethylaminoethyl methacrylate and 1-bromooctane are added to a three-necked flask and stirred, and reacted at room temperature for 12-14 hours, followed by post-treatment to obtain the antibacterial agent.

2. The antiviral water-based paint for interior walls according to claim 1, characterized in that, The dispersant is polyethylene glycol 400, the wetting agent is sodium butylnaphthalene sulfonate, the defoamer is defoamer GP-330, and the thickener is thickener SN-612; the ratio of the amount of hydroxypropyl acrylate, butyl acrylate, acrylic acid, antibacterial agent, modified zinc oxide, silicone microemulsion, and initiator solution is 7-8g:3-4g:2-3g:4-5g:1.6-2.3g:50-60mL:2g, and the stirring speed is 800-1000r / min.

3. The antiviral water-based paint for interior walls according to claim 1, characterized in that, The weight ratio of diethylaminoethyl methacrylate to 1-bromooctane is 2:

3.

4. The antiviral water-based paint for interior walls according to claim 1, characterized in that, The modified zinc oxide is prepared by adding nano zinc oxide, anhydrous ethanol and sorbic acid into a three-necked flask, ultrasonically dispersing for 30-50 min, then stirring, raising the temperature of the three-necked flask to 60-65℃, and maintaining the temperature for 10-12 h. After post-treatment, modified zinc oxide is obtained. The ratio of nano zinc oxide, anhydrous ethanol and sorbic acid is 10g:100mL:0.8-1.2g, and the particle size of the nano zinc oxide is 10-20μm.

5. The antiviral water-based paint for interior walls according to claim 1, characterized in that, The ratio of methylvinyldiethoxysilane, octamethylcyclotetrasiloxane, emulsion and catalyst is 2g:5g:50-60mL:0.5g, and the stirring speed is 800-1000r / min.

6. The antiviral water-based paint for interior walls according to claim 1, characterized in that, The activated filler is obtained by the following steps: A1. Add the filler and inorganic pigment to a ball mill, ball mill, and then pass through an 800-mesh sieve to obtain a mixed filler; A2. Add the mixed packing material, anhydrous ethanol, and KH-560 to a three-necked flask and ultrasonically disperse for 30-50 minutes. Then, stir and raise the temperature of the three-necked flask to 55-65℃. Add the catalyst solution to the three-necked flask and keep it at this temperature for 40-60 minutes. The activated packing material is then obtained through post-treatment.

7. The antiviral water-based paint for interior walls according to claim 6, characterized in that, In step A1, the weight ratio of the filler to the inorganic pigment is 6-8:1, and the filler is composed of kaolin and talc in a weight ratio of 3:1; in step A2, the ratio of the mixed filler, anhydrous ethanol, KH-560 and catalyst solution is 5g:50mL:2g:7mL, and the catalyst solution is a 0.1-0.3mol / L sodium hydroxide solution.

8. A method for preparing an antiviral water-based paint for interior walls according to any one of claims 1-7, characterized in that, Includes the following steps: S1. According to the formula, add the antibacterial and antiviral emulsion into a three-necked flask and stir. Add the dispersant, wetting agent, defoamer, thickener and activating filler to the three-necked flask in sequence and stir for 30-50 minutes to obtain the crude water-based paint. S2. Transfer the coarse water-based paint to a sand mill and grind it at high speed to obtain a water-based paint with a fineness of 20-25μm.

Images