CN113185882A

CN113185882A - Antiviral anti-formaldehyde coating and preparation method thereof

Info

Publication number: CN113185882A
Application number: CN202110602881.4A
Authority: CN
Inventors: 黄凤丽; 张晓红; 张喜强; 欧广源
Original assignee: China Paints Shenzhen Co ltd
Current assignee: China Paints Shenzhen Co ltd
Priority date: 2021-05-31
Filing date: 2021-05-31
Publication date: 2021-07-30

Abstract

The application belongs to the technical field of coatings, and particularly relates to an antiviral and anti-formaldehyde coating and a preparation method thereof. The antiviral and formaldehyde-resistant coating comprises the following raw material components in percentage by mass of 100 percent: antiviral anti-formaldehyde emulsion: 35-50%, pigment: 12-25%, coalescent: 1.0-2.5%, thickener: 0.3-0.5%, dispersant: 0.6-1.5%, wetting agent: 0.2-0.5%, defoamer: 0.5-0.8%, freeze-thaw resistant stabilizer: 0.5-1.5%, preservative: 0.2-0.3%, pH regulator: 0.1-0.2% and 12-20% of water. The antiviral and anti-formaldehyde coating has excellent antiviral, antibacterial and anti-formaldehyde functions, meets the GB/9756 performance index requirements of the coating, and meets the harmful substance release standard A + requirements of JG/T481 water-based interior wall coating materials.

Description

Antiviral anti-formaldehyde coating and preparation method thereof

Technical Field

The application belongs to the technical field of coatings, and particularly relates to an antiviral and anti-formaldehyde coating and a preparation method thereof.

Background

At present, the antiviral paint generally adopts the method of additives, such as copper ions, silver ions, quaternary ammonium salts and other additives, and destroys the cell wall of bacteria, nucleic acid of virus or biological enzymeThe transmission of (A) achieves the antibacterial and antiviral effects. The method of the additive is easily influenced by the covering and dispersion of the emulsion and the filler in the system, has the phenomena of instability and uneven distribution, has low utilization efficiency, easily causes the reduction of antibacterial and antiviral efficacies and the deterioration of the durability of storage influence, and adopts the coating made of the additive, Ag⁺、Cu⁺The plasma is easy to migrate to the surface, and the human body is harmed by oral contact. At present, most of the formaldehyde-resistant coatings are prepared by adopting common emulsion or formaldehyde-resistant emulsion, formaldehyde-removing additives, such as nano zinc oxide, nano titanium dioxide, bamboo charcoal powder, formaldehyde-removing powder or formaldehyde-removing spray and antiviral additive raw materials, and the formaldehyde-removing principle is that formaldehyde-removing functional groups of the coatings react with formaldehyde in the air to generate water so as to achieve the purpose of purifying formaldehyde. However, the common formaldehyde-resistant emulsion has the phenomena of large smell and easy yellowing, the formaldehyde-removing additive has strong activity, is unstable and unevenly distributed in a system, such as nano zinc oxide and nano titanium dioxide, and the problem of thickening after storage is easily caused, and the formaldehyde-removing effect is easily influenced by light and uneven distribution, and the formaldehyde-removing function can be exerted to the maximum by assistance under the condition of ultraviolet rays, so that the problems of poor effect and non-durability are caused; the bamboo charcoal powder only has an adsorption effect, can be released again when reaching a saturated state and meeting an air humid environment, and has an undesirable and long-lasting effect; the additive formaldehyde-resistant powder and the formaldehyde-resistant spray have the problems of reduced function and stability after thermal storage, and the effect and the durability are greatly reduced.

At present, most of antiviral and formaldehyde-resistant coatings are prepared by mutually compounding an anti-formaldehyde emulsion or a common emulsion, a formaldehyde-removing additive and an antiviral additive, and the physically mixed and compounded type formaldehyde-resistant and antiviral additive has the problems of low utilization rate, large dosage, easy oxidation, discoloration, ion migration and the like, and is easy to cause the problems of poor effect, non-persistence, poor safety and the like due to the influence of uneven light and distribution.

Disclosure of Invention

The application aims to provide an antiviral and anti-formaldehyde coating and a preparation method thereof, and aims to solve the problems that the existing antiviral or anti-formaldehyde coating is in a physical mixed compound type, and the antiviral or anti-formaldehyde effect is poor in stability and not durable to a certain extent.

In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:

in a first aspect, the application provides an antiviral and anti-formaldehyde coating, which comprises the following raw material components in percentage by mass, based on 100% of the total mass of the raw material components of the antiviral and anti-formaldehyde coating:

the antiviral and anti-formaldehyde emulsion is an acrylate polymer containing an anti-formaldehyde group and an antibacterial group.

In a second aspect, the present application provides a method for preparing an antiviral and formaldehyde-resistant coating, comprising the following steps:

preparing an acrylate polymer containing an anti-formaldehyde group and an antibacterial group to obtain an antiviral anti-formaldehyde emulsion;

mixing and dispersing the antiviral and anti-formaldehyde emulsion, the pigment, the filler, the film-forming additive, the thickening agent, the dispersing agent, the wetting agent, the defoaming agent, the anti-freeze-thaw stabilizer, the in-tank preservative, the pH regulator and the water according to the formula ratio to obtain the antiviral and anti-formaldehyde coating.

According to the antiviral and anti-formaldehyde paint provided by the first aspect of the application, a paint film prepared by mixing and dispersing raw material components in the antiviral and anti-formaldehyde paint has the functions of resisting viruses, bacteria, formaldehyde, discoloration and the like through the synergistic effect of the raw material components. Compared with a paint film prepared by physically mixing additives, the antiviral and anti-formaldehyde emulsion is more stable, and the antiviral and anti-formaldehyde emulsion is more firmly combined in the curing process of the paint film, so that the decline of the antibacterial, antiviral and anti-formaldehyde efficiency caused by leaching or loss of active ingredients is prevented; the drug does not cause safety problems and drug resistance because excessive active ingredients are enriched on the surface and are orally contacted with the human body. And has excellent discoloration resistance.

The preparation method of the antiviral and anti-formaldehyde coating provided by the second aspect of the application has a simple preparation process, is suitable for industrial large-scale production and application, and the prepared antiviral and anti-formaldehyde coating has the functions of resisting viruses, bacteria, formaldehyde, discoloration and the like through the synergistic effect of the raw material components, and has stability and durability of the antiviral and antibacterial effect of formaldehyde.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a graph of the antimicrobial and leaching tests provided in example 1 and comparative example 1 of the present application.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.

The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.

The first aspect of the embodiment of the application provides an antiviral and formaldehyde-resistant coating, which comprises the following raw material components in percentage by mass, based on 100% of the total mass of the raw material components of the antiviral and formaldehyde-resistant coating:

wherein, the antivirus anti-formaldehyde emulsion is an acrylate polymer containing an anti-formaldehyde group and an antibacterial group.

The antiviral and anti-formaldehyde coating provided by the first aspect of the application adopts an antiviral and anti-formaldehyde emulsion as a main raw material component, wherein the antiviral and anti-formaldehyde emulsion is an acrylate polymer containing an anti-formaldehyde group and an antibacterial group, and the antibacterial group can destroy the cell wall of bacteria and the transmission of nucleic acid or biological enzyme of viruses, so that the antibacterial and antiviral effects are achieved. The formaldehyde-resistant functional group can adsorb free formaldehyde in the air and perform irreversible chemical combination reaction with the formaldehyde so as to achieve the purpose of purifying the formaldehyde, and the formaldehyde-resistant functional group is copolymerized into the acrylate polymer, so that the effective utilization rate is high, the assistance and influence of external conditions are not needed, the formaldehyde removal efficiency is higher and more durable, and the formaldehyde is not easy to yellow. Therefore, the antiviral and anti-formaldehyde emulsion enables the coating to have the functions of resisting bacteria, viruses and formaldehyde, and the antibacterial, antiviral and anti-formaldehyde effects are realized by a chemical combination mode, so that the stability and the durability of the antibacterial, antiviral and anti-formaldehyde effects of the coating are improved. In addition, the raw material components of the antiviral and formaldehyde-resistant coating, such as pigment, filler, dispersant, wetting agent, defoamer, film-forming aid, anti-freeze-thaw stabilizer, preservative, deionized water and the like, improve the dispersion stability and film-forming property of the antiviral and formaldehyde-resistant coating slurry. If the content of each raw material component is too high, the stability, corrosion resistance, viscosity, washing resistance and the like of the coating are reduced, and if the content of each raw material component is too low, the raw material components cannot play a corresponding effect in the coating, and all functions of the coating are reduced. According to the embodiment of the application, a paint film prepared by mixing and dispersing the raw material components in the antiviral and formaldehyde-resistant paint has the functions of resisting viruses, bacteria, formaldehyde, discoloration and the like through the synergistic effect of the raw material components. Compared with a paint film prepared by physically mixing additives, the antiviral and anti-formaldehyde emulsion is more stable, and the antiviral and anti-formaldehyde emulsion is more firmly combined in the curing process of the paint film, so that the decline of the antibacterial, antiviral and anti-formaldehyde efficiency caused by leaching or loss of active ingredients is prevented; there is no concern about safety problems and drug resistance due to excessive active ingredient enrichment on the surface to come into oral contact with the human body. The paint has excellent discoloration resistance, meets the requirement of GB/9756 performance index of the paint, meets the requirement of the standard A + of the release amount of harmful substances of JG/T481 water-based interior wall coating materials, is green and environment-friendly, and can be widely applied to indoor wall coating.

In some embodiments, the antimicrobial groups comprise: at least one of silver ions and copper ions; these antibacterial groups can destroy the cell wall of bacteria and the transmission of nucleic acid or biological enzyme of virus, so as to reach the antibacterial and antiviral effect.

In some embodiments, the anti-formaldehyde group comprises: at least one of amido and amido, the formaldehyde-resistant groups can react with free formaldehyde in the air irreversibly to produce harmless water, so as to achieve the purpose of purifying formaldehyde.

In some embodiments, the mass percent of anti-formaldehyde groups in the acrylate polymer is from 2 to 10%; the mass percentage of the antibacterial group is 0.05-0.5%, the content of the functional group in the acrylate polymer ensures that the emulsion simultaneously plays the roles of resisting formaldehyde and bacteria in the coating, and the components jointly act synergistically to achieve the effects of optimal function and performance, best stability effect and more lasting function. In some embodiments, the acrylate polymer preferably has a formaldehyde resistant group content of 3% and an antimicrobial group content of 0.3%.

In some embodiments, the antiviral, anti-formaldehyde emulsion is an acrylate polymer containing amine groups and silver ions. In the antiviral and anti-formaldehyde coating provided by the embodiment of the application, silver ions in the antiviral and anti-formaldehyde emulsion can destroy cell walls of bacteria and transmission of nucleic acid or biological enzyme of viruses, so that the antibacterial and antiviral effects are achieved, amino groups can react with free formaldehyde in the air irreversibly to produce harmless water, so that the purpose of purifying formaldehyde is achieved, and by adopting the antiviral and anti-formaldehyde emulsion, the double-anti-cavity emulsion can simultaneously meet the antibacterial, antiviral and anti-formaldehyde functions. Meanwhile, the emulsion has low odor, ultralow VOC and formaldehyde, so that the coating has low VOC, and the emulsion can play a main film forming substance through the synergistic effect with other components, so that a paint film of the coating has excellent scrubbing resistance, and the comprehensive performance of the coating is comprehensively improved.

In some embodiments, the pigment comprises: at least one of rutile type titanium dioxide and anatase type titanium dioxide; the pigments have excellent covering and dispersing properties, and provide good paint film color intensity and covering power in the coating process of the paint, wherein the anatase titanium dioxide has high whiteness and stronger covering power.

In some embodiments, the filler comprises: at least one of calcined kaolin, ground calcium carbonate, diatomite, mica powder and talcum powder; the calcined kaolin such as snow white and the like has high whiteness and strong covering power, can improve the covering power of a dry film and reduce the using amount of pigments such as titanium white and the like in the coating, and simultaneously has good dispersibility and fluidity and improves the stability of the product. Wherein, the heavy calcium carbonate can be any one or more than two of 600 meshes, 800 meshes and 1250 meshes, the dense paint film effect can be provided by adopting different meshes, the heavy calcium carbonate has good filling property and dispersion property, and the manufacturer of the heavy calcium carbonate can be Jiangxi Guangyuan or Guangxi Haoyu. The diatomite has a porous structure, can reduce the gloss of a paint film and enable the paint film to have a matte effect, and manufacturers of the diatomite can select EP MINERALS Celabrite, talcum powder and mica powder sheet structures in the United states, so that a compact paint film effect can be formed.

In some embodiments, the coalescent includes: at least one of triethylene glycol di (2-ethylhexanoate), dibasic acid ester, alcohol ether with a boiling point of 286-310 ℃ and alcohol ether ester with a boiling point of 286-310 ℃. In some embodiments, the coalescent is selected from: at least one of German Eurasian OXFLM 351CN, Shengxing line SH LOCA DA, Shengxing line SH LOCA A +, English Chemoxy coast 290Plus, Istman Eastman Optifilm Enhancer 300, Runtai chemical RUNTAI RTC-290A; the film forming auxiliary agents have high boiling point, ultralow odor and high film forming efficiency, meet the requirement of low release A + standard, are beneficial to the film forming performance of the coating when added into the coating, and are green and environment-friendly.

In some embodiments, the freeze-thaw resistance stabilizer comprises: at least one of Solvaviolide FT-100XTRIM, Akzonobel ETHYLAN BCD 42A, Dow FT-893, BASF FT68, Lubrizol HPA GRB 8; the freeze-thaw resistant stabilizer can improve the freeze-thaw stability of a coating system, improve the application performance of the coating in a low-temperature environment, contribute to improving the open time and the color development of the coating, does not contain APEO (alkylphenol polyoxyethylene ether compounds), has low/zero VOC, and is green and environment-friendly.

In some embodiments, the thickening agent comprises: at least one of hydroxyethyl cellulose and polyurethane thickener. In some embodiments, the thickener is selected from hydroxyethyl cellulose with the molecular weight of 1.5K to 30K, or a solvent-free and organic tin-free polyurethane thickener, wherein the hydroxyethyl cellulose with the molecular weight of 1.5K has good biological enzyme resistance, leveling property and fluidity; the 30K hydroxyethyl cellulose has good biological enzyme resistance, the thickening efficiency is higher than 1.5K, and the cost can be reduced; the polyurethane thickener has excellent flowability, leveling property and splashing resistance. In some embodiments, the thickener may be at least one of LOTTE cellulose B30K, LOTTE cellulose B15K, Ashland nature 250HBR, Shin-Etsu TyloseHS30000YP2, DOW ACRYSOL RM-3030, DOW ACRYSOL RM-725, DOW ACRYSOL RM-12W, BASF rhevis PE1331, BASF rhevis PU 1341.

In some embodiments, the dispersant comprises: at least one of a sodium salt aqueous solution of a carboxylic acid polymer and an acrylic acid sodium salt dispersant, wherein the sodium salt aqueous solution of the carboxylic acid polymer is a high-efficiency dispersant for inorganic fillers and pigments and can improve wet scrub resistance and anti-blocking property; the sodium acrylate dispersant has the characteristics of high dispersing power and low odor, and has good stability, dispersibility and color development property when being matched for use. In some embodiments, the dispersant comprises: at least one of BASF DISPEX CX 4320, BASF DISpex AA4140AS, DOW OROTAN 731A, BASF SOKALAN PA 25X, NOPCO SN-5040.

In some embodiments, the wetting agent is selected from nonionic surfactants, which provide good wetting of the substrate, reduction of surface tension, and stabilization. In some embodiments, the wetting agent is selected from: at least one of Dow ECOSURF BD-109, Clariant GENAPOL X080 and Clariant EMULSOGEN LCN 407.

In some embodiments, the defoaming agent is selected from: at least one of modified organic silicon defoaming agent and mineral oil defoaming agent. In some embodiments, the defoaming agent is selected from: at least one of BlackBURN DISPELAIR CF 18441, BlackBURN DISPELAIR CF 13635, BASF Foamastar ST 2410AC, NOPCO SN-DEFAOAMER 1340, and NOPCO NXZ; the defoaming agents are free of solvents, have a high-efficiency foam control effect, can effectively inhibit and defoam foams, and reduce the generation of foams in a tank so as to avoid the influence on the appearance of the coating and avoid paint film defects caused by the foams in the construction process, such as craters, pinholes and the like.

In some embodiments, the preservative is selected from: at least one of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4-isothiazolin-3-one (MIT), benzisothiazolin-3-one (BIT), 2-dibromo-3-cyanopropionamide; the antiseptic has broad-spectrum bactericidal effect, can prolong the storage time of the paint, is not easy to deteriorate, does not contain formaldehyde and formaldehyde releaser, and has no VOC. In some embodiments, the preservative is selected from: at least one of Turker THOR ACTICIDE MBS, Turker THOR ACTICIDE RS CONC, Turker THOR ACTICIDE MBS5050, Longsha LONZA PROXEL 130S, Longsha LONZA PROXEL MB, Wenke VINkocide CMI 3.0.

In some embodiments, the pH adjuster is selected from at least one of a multifunctional pH adjuster of an aqueous silane silicone solution, a multifunctional amine adjuvant, KOH, NaOH, wherein the multifunctional pH adjuster of the aqueous silane silicone solution is odorless, solvent free, VOC free while having excellent stability and helping to improve scrub resistance; KOH and NaOH have no odor and VOC, high pH adjusting efficiency and low cost; the multifunctional amine assistant has stable pH value regulation, wetting and dispersing functions, certain amine smell and low requirement on smell. In some embodiments, the pH adjusting agent is selected from: watt WACKER SILRES BS 168, Dow APM-95, KOH, NaOH, preferably watt SILRES BS 168.

The antiviral and anti-formaldehyde paint provided by the embodiment of the application can be prepared by the method of the following embodiment.

The second aspect of the embodiments of the present application provides a preparation method of the above antiviral and anti-formaldehyde coating, comprising the preparation steps of:

s10, preparing an acrylate polymer containing an anti-formaldehyde group and an antibacterial group to obtain an antiviral anti-formaldehyde emulsion;

s20, mixing and dispersing the antiviral and anti-formaldehyde emulsion, the pigment, the filler, the film forming aid, the thickening agent, the dispersing agent, the wetting agent, the defoaming agent, the freeze-thaw resistant stabilizer, the preservative in the tank, the pH regulator and water according to the formula ratio to obtain the antiviral and anti-formaldehyde coating.

According to the preparation method of the antiviral and anti-formaldehyde coating provided by the second aspect of the application, the acrylate polymer containing the anti-formaldehyde group and the antibacterial group is prepared, the anti-formaldehyde group and the antibacterial group are anchored on the acrylate polymer in a chemical combination mode, so that the falling, loss and the like of active ingredients are prevented, and the stability and durability of the coating in formaldehyde resistance, bacteria resistance and virus resistance are improved. Then, the antivirus and anti-formaldehyde emulsion, the pigment, the filler, the film forming additive, the thickening agent, the dispersing agent, the wetting agent, the defoaming agent, the anti-freeze thawing stabilizer, the preservative in the tank, the pH regulator and the water in the formula are mixed and dispersed to obtain the antivirus and anti-formaldehyde coating. The prepared antiviral and anti-formaldehyde coating has the functions of resisting viruses, bacteria, formaldehyde, discoloration and the like through the synergistic effect of the raw material components, and the stability and the durability of the antiviral and antibacterial effect of the formaldehyde meet the requirement of GB/9756 performance indexes of the coating, meet the requirement of the release standard A + of harmful substances of JG/T481 water-based interior wall coating materials, are green and environment-friendly, and can be widely applied to indoor wall coating.

In some embodiments, the step of preparing the acrylate polymer having an anti-formaldehyde group and an antibacterial group in the step S10 described above includes: mixing acrylamide, acrylic acid, hydroxyethyl methacrylate, butyl acrylate, an antibacterial component, an initiator, an emulsifier and a solvent, and then reacting to obtain the acrylate polymer containing the formaldehyde group and the antibacterial group. According to the embodiment of the application, acrylamide, acrylic acid, hydroxyethyl methacrylate and butyl acrylate are used as reaction monomers, and are subjected to polymerization and coupling reaction with an antibacterial component with an active group under the action of an initiator, an emulsifier, a solvent and the like to generate an acrylate polymer which has an amino group or an amino group and other formaldehyde-resistant groups and is anchored with the antibacterial group, so that the formaldehyde-resistant antibacterial emulsion is obtained.

In some embodiments, the mass ratio of acrylamide, acrylic acid, hydroxyethyl methacrylate, butyl acrylate, emulsifier, antibacterial component, initiator and solvent is (2-15): (8-12): (15-25): (15-20): (0.05-0.15): (0.3-0.8): (2-5): (45-50), each raw material component has better crosslinking effect under the mixture ratio, the purity of the polymer product is high, and the by-product is less.

In some embodiments, the solvent is selected from water.

In some embodiments, the emulsifier is selected from silicone emulsifiers.

In some embodiments, the initiator is selected from t-butyl hydroperoxide. In some embodiments, the initiator is selected from t-butyl hydroperoxide at a concentration of 2% by mass.

In the above embodiments, the solvent, the emulsifier, and the initiator are more favorable for the cross-linking polymerization between the monomer and the antibacterial component.

In some embodiments, the antimicrobial component includes silver diaminehydroxide, and the silver ions in the antimicrobial component provide antimicrobial efficacy to the emulsion, thereby providing both antimicrobial and antiviral effects to the emulsion.

In some embodiments, 48.4% by weight of water is used as a solvent system, 5% of acrylamide, 10% of acrylic acid, 15% of hydroxyethyl methacrylate and 18% of butyl acrylate are used as main monomers, 0.1% of silicone emulsifier, 0.5% of diamine hydroxide silver is used as a functional assistant, and 3% of tert-butyl hydroperoxide is used as an initiator, and the emulsion is polymerized to synthesize amine-bearing emulsion and is subjected to coupling reaction to anchor silver ions on an acrylate polymer, so that the emulsion simultaneously has antibacterial, antiviral and formaldehyde-resistant effects.

In some embodiments, 5kg of acrylamide, 10kg of acrylic acid, 15kg of hydroxyethyl methacrylate, 18kg of butyl acrylate and 0.1kg of silicone emulsifier are uniformly mixed to obtain a mixed monomer; then adding 48.4kg of water into a reaction kettle, heating to 55 ℃ while stirring, adding 20kg of mixed monomer, adding 0.5kg of tert-butyl hydrogen peroxide aqueous solution with the mass percent concentration of 2%, then synchronously and slowly adding the rest of mixed monomer and 2.5kg of tert-butyl hydrogen peroxide aqueous solution with the mass percent concentration of 2% dropwise for polymerization reaction to generate acrylic ester polymer with amino groups, finally adding 0.5kg of diamine hydroxide silver, and anchoring silver ions on the acrylic ester polymer through coupling reaction to obtain the formaldehyde-resistant antiviral acrylic ester polymer.

In some embodiments, in the step S20, the step of mixing and dispersing includes:

s21, performing first mixing and dispersing treatment on water, a dispersing agent, a wetting agent and a defoaming agent in the amounts of 50-80% and 30-50% respectively;

s22, adding the pigment and the filler according to the formula amount to perform second mixing and dispersing treatment;

s23, adding 25-40% of thickener, 5-10% of water and 5-10% of pH regulator for third mixing and dispersing treatment.

S24, adding the antiviral and anti-formaldehyde emulsion in the formula amount to perform fourth mixing and dispersing treatment;

and S25, adding the balance of the defoaming agent, the balance of the film-forming aid, the balance of the thickening agent, the balance of the freeze-thaw resistance stability, the balance of the preservative and the balance of water, and performing fifth mixing treatment to obtain the antiviral and formaldehyde-resistant paint.

The coating comprises a coating body, a coating layer, a coating agent, a dispersing agent, a wetting agent, a part of defoaming agent, a pigment, a filler, a pH regulator, an antiviral anti-formaldehyde emulsion, a residual defoaming agent, a film forming assistant, a thickening agent, freeze-thaw resistance stability, a preservative and water. Wherein, the defoaming agent is added twice before and after, which can better inhibit the generation of bubbles in the dispersion process of the inner wall slurry and eliminate the foams generated by mixing, dispersing and stirring. And adding water for three times, wherein the first time is used for dispersing and dissolving the components of the raw materials, the second time is used for diluting or premixing the water solution of the thickening agent, the conditions that the local thickening causes the generation of particles and the overload of a dispersion machine are avoided, and then, the optimal viscosity is adjusted by adding the residual water again, so that the components reach a stable state, and the sedimentation is prevented. The preparation method of the antiviral and formaldehyde-resistant coating provided by the application is simple in process, the components are added according to the adding sequence and process of the embodiment, the uniform and stable dispersion of the slurry can be ensured, the covering power is high, the chroma of the paint film is good, the storage stability of the system is high, the paint film can be stored for more than 3 years, the long-term defoaming property is good, the paint film after implementation has no defects of pinholes, craters and the like, the leveling property is good, the function is durable, and the effect is maximized. The proportion range of each component can be adjusted according to the requirement of performance grade.

In some embodiments, the conditions of the first mixing dispersion process include: under the condition that the rotating speed is 400-600 rpm, water, a dispersing agent, a wetting agent and a defoaming agent are added in sequence, and the dispersing agent, the wetting agent and the defoaming agent are dispersed for 2-3 minutes, so that the dispersing agent, the wetting agent and the defoaming agent are mixed with part of water according to the formula amount to form slurry.

In some embodiments, the step of the second mixing dispersion process comprises: and adding the pigment and the filler under the condition that the rotating speed is 500-700 rpm, dispersing for 2-4 minutes, and circularly dispersing the pigment and the filler in the slurry after the first mixing and dispersing treatment under the condition.

In some embodiments, in step S23, after a thickener in an amount of 25 to 40% by weight and water in an amount of 5 to 10% by weight are mixed to form a mixed solution, the mixed solution and a pH adjuster are added to the product after the second mixing treatment, and a third mixing and dispersing treatment is performed.

In some embodiments, the step of the third mixing and dispersing process comprises: under the condition that the rotating speed is 1600-1800 rpm, a thickening agent, water and a pH regulator are added, dispersion treatment is carried out for 20-30 minutes, the viscosity of the slurry is increased to reach the optimal dispersion state, the pH value is adjusted, the pH regulator is dispersed in the slurry after the second mixing and dispersing, the raw material components are fully contacted and dispersed, the stable state is reached, and the particle size of the slurry reaches the fineness requirement.

In some embodiments, the step of the fourth mixing and dispersing process comprises: and adding the antiviral and anti-formaldehyde emulsion under the condition that the rotating speed is 800-900 rpm, and performing dispersion treatment for 2-4 minutes to rapidly disperse the antiviral and anti-formaldehyde emulsion in the slurry after the third mixing treatment.

In some embodiments, the step of fifth mixing dispersion processing comprises: and under the condition that the rotating speed is 800-900 rpm, sequentially adding the defoaming agent, the film forming aid, the thickening agent, the freeze-thaw resistance stability, the preservative and the balance of water, dispersing for 10-15 minutes to quickly and uniformly disperse the components such as the defoaming agent, the film forming aid, the thickening agent, the freeze-thaw resistance stability, the preservative and the like in the slurry after the fourth mixing and dispersing treatment, and further dispersing and mixing the raw material components in the coating to form the coating with stable dispersion.

The above embodiments of the application combine the characteristics of the raw material components, adopt different sequences and different dispersion mixing rotating speeds and times, and avoid the phenomenon that the paint film has dark hue and low viscosity due to overlong dispersion time of some components in the paint; meanwhile, the problems that the dispersion time of certain components in the coating is too short, the dispersion stability of slurry is poor, the particle size/fineness can not meet the requirement, the covering power can not meet the expected requirement, the hand feeling of a paint film is poor, coagulation occurs in long-time storage and the like are avoided. In addition, the stirring speed is controlled, so that the conditions of emulsion breaking, long-term defoaming deterioration, long-term preservative performance deterioration caused by overhigh stability (more than 60 ℃) and the like caused by excessive dispersion are avoided.

In order to make the details and operations of the above-mentioned embodiments of the present application clearly understood by those skilled in the art and to make the progress of the anti-viral and anti-formaldehyde coating and the preparation method thereof obvious, the above-mentioned technical solutions are illustrated by the following examples.

The preparation steps of the antiviral and anti-formaldehyde emulsion in the following embodiments 1-3 comprise: 5kg of acrylamide, 10kg of acrylic acid, 15kg of hydroxyethyl methacrylate, 18kg of butyl acrylate and 0.1kg of silicone emulsifier are uniformly mixed to obtain a mixed monomer; then adding 48.4kg of water into a reaction kettle, heating to 55 ℃ while stirring, adding 20kg of mixed monomer, adding 0.5kg of tert-butyl hydrogen peroxide aqueous solution with the mass percent concentration of 2%, then synchronously and slowly adding the rest of mixed monomer and 2.5kg of tert-butyl hydrogen peroxide aqueous solution with the mass percent concentration of 2% dropwise for polymerization reaction to generate acrylic ester polymer with amino groups, finally adding 0.5kg of diamine hydroxide silver, and anchoring silver ions on the acrylic ester polymer through coupling reaction to obtain the formaldehyde-resistant antiviral acrylic ester polymer.

Example 1

The antiviral and formaldehyde-resistant coating comprises 100% of raw material components by weight, and the raw material components, the process steps and the conditions are shown in the following table 1:

TABLE 1

Example 2

The antiviral and formaldehyde-resistant coating comprises 100 percent of total weight, and the content of the raw material components, the process steps and the conditions are shown in the following table 2:

TABLE 2

Example 3

The antiviral and formaldehyde-resistant coating comprises 100 percent of total weight, and the following raw material components, process steps and conditions are shown in the following table 3:

TABLE 3

Comparative example 1

Antiviral healthy plant water paint VIT2018

Comparative example 2

King seed silver ion children paint

Comparative example 3

BB oxygen bar antiviral children wall paint

Further, in order to verify the advancement of the examples of the present application, the following performance tests were performed on the antiviral and anti-formaldehyde coating prepared in example 1 and the coatings of comparative examples 1 to 3:

and (4) testing standard:

functionality (one):

GB/T21866-;

BS ISO21702-2019 determination of antiviral Activity on Plastic and other non-porous surfaces

JC/T1074-2008 'requirement on Performance of coating Material for indoor air purification function'

GB/T1741-2007 method for determining the resistance to mildew of paint films

(II) performance: GB/T9756-2018 synthetic resin emulsion interior wall coating

(III) safety:

GB18582-2020 Limited amount of harmful substances in wall paint for Chinese architecture

HJ2537-2014 Water-based paint for environmental Mark product technical requirement

JG/T481-2015 aqueous interior wall coating material with low Volatile Organic Compounds (VOC)

The results of the functionality tests are shown in table 4 below:

TABLE 4

Example 1 antimicrobial and leaching test of antiviral and Formaldehyde-resistant coating and comparative example 1 coating:

halo assay (qualitative) was used: test bacteria are inoculated on an agar culture medium, the test bacteria are tightly attached to a sample, the culture is carried out for 24 hours at 37 ℃, and then the propagation condition of the bacteria and the size of a halo in a sterile area around the sample are observed by a magnifying glass. As shown in figure 1: FIG. 1 (left) shows the test results of example 1 of the present application, with active portion under the substrate, but no active substance leached, FIG. 1 (right) shows the test results of comparative example 1, with active portion under the substrate, and with active substance leached (as indicated by the arrow in the right of FIG. 1, i.e., leached active substance), as can be seen from FIG. 1: the antiviral and anti-formaldehyde coating in the embodiment 1 has more excellent antibacterial activity, no active substance is leached, the surface concentration of silver ions is effectively controlled, and the coating is safer and more environment-friendly and has longer efficacy.

Example 1 antiviral test results for an antiviral, anti-formaldehyde coating are shown in table 5 below:

TABLE 5

The performance and safety test results of the antiviral and formaldehyde-resistant coatings of examples 1-3 are shown in the following tables 6-8:

TABLE 6 paint Performance test

Note: the indexes of washing resistance and covering power can be adjusted and matched according to the provided formula range to meet the standard grade requirement

TABLE 7 Limit requirements for hazardous substances

Note: the minimum detection limit of the total lead (Pb) content and the soluble heavy metal is 5mg/kg, the minimum detection limit of the metal content (hexavalent chromium) is 1.0mg/kg, the minimum detection limit of the total content of the benzene series is 50mg/kg, the minimum detection limit of VOC is 2g/L, and the minimum detection limit of free formaldehyde is 5 mg/kg.

TABLE 8 amount of harmful substance released

According to the test results, the antiviral and anti-formaldehyde coating in the embodiment 1-3 can meet the antibacterial and antifungal standards and the antiviral standard, simultaneously meet the anti-formaldehyde standard, and have antibacterial property and durability of over 99.99% for various bacteria; the mildew resistance and the durability of various moulds reach the 0-grade (highest-grade) requirement, the influenza A virus (H3N2), the coronavirus, the feline calicivirus, the enterovirus (71 type) and the like are resisted, and the antiviral rate reaches over 99.99 percent within 2 hours; the formaldehyde purification efficiency reaches more than 90%, and the durability reaches more than 90%, which is better than the standard requirement (the standard requirement is that the formaldehyde purification efficiency is more than or equal to 75%, and the durability is more than or equal to 60%). Compared with comparative examples 1-3, the method has the following advantages: a. compared with the coating prepared by compounding the additive, the antibacterial and antiviral effect is more stable, the effective components of silver ions are effectively controlled and can be uniformly distributed on the surface of a paint film, the aims of high-efficiency antibacterial and antiviral are achieved, the active substances are not leached, the problem of migration is avoided, and the efficiency is longer. b. Compared with the coating prepared by compounding the additives in comparative examples 1-3, the coating has the advantages of no need of photocatalysis and limitation by external conditions, more stable performance, difficult yellowing and more prominent and lasting formaldehyde removal effect. c. Meets the requirement of GB/9756 performance index of the coating. d. The coating is safe and environment-friendly, meets the requirements of the limited standard of hazardous substances and the release A + of JG/T481 aqueous interior wall coating materials, and is environment-friendly. The environment-friendly indoor wall can be widely applied to indoor walls, particularly places with high environmental protection requirements such as hospitals and schools, can prevent the harm of bacteria, mold and viruses, and simultaneously purifies free formaldehyde in air to create a healthy home environment for people.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. The antiviral and anti-formaldehyde coating is characterized by comprising the following raw material components in percentage by mass, based on 100% of the total mass of the raw material components of the antiviral and anti-formaldehyde coating:

35 to 50 percent of antiviral and anti-formaldehyde emulsion,

12 to 25 percent of pigment,

10 to 35 percent of filler,

1.0 to 2.5 percent of film-forming additive,

0.3 to 0.5 percent of thickening agent,

0.6 to 1.5 percent of dispersant,

0.2 to 0.5 percent of wetting agent,

0.5 to 0.8 percent of defoaming agent,

0.5 to 1.5 percent of freeze-thaw resistant stabilizer,

0.2 to 0.3 percent of preservative,

0.1 to 0.2 percent of pH regulator,

12 to 20 percent of water;

wherein, the antivirus and anti-formaldehyde emulsion is an acrylate polymer containing an anti-formaldehyde group and an antibacterial group.

2. The antiviral, anti-formaldehyde coating of claim 1, wherein said antibacterial groups comprise: at least one of silver ions and copper ions;

and/or, the anti-formaldehyde group comprises: at least one of an amine group and an amino group.

3. The antiviral and anti-formaldehyde coating according to claim 2, wherein the mass percentage of the anti-formaldehyde group in the acrylate polymer is 2-10%; the mass percentage of the antibacterial groups is 0.05-0.5%.

4. The antiviral, anti-formaldehyde coating of claim 3, wherein said pigment comprises: at least one of rutile type titanium dioxide and anatase type titanium dioxide;

and/or, the filler comprises: at least one of calcined kaolin, ground calcium carbonate, diatomite, mica powder and talcum powder;

and/or, the coalescent comprises: at least one of triethylene glycol di (2-ethylhexanoate), dibasic acid ester, alcohol ether with a boiling point of 286-310 ℃ and alcohol ether ester with a boiling point of 286-310 ℃;

and/or, the freeze-thaw resistance stabilizer comprises: at least one of Rhodoline FT-100XTRIM, Akzonobel ETHYLAN BCD 42A, DOW FT-893, BASF FT68, Lubrizol HPA GRB 8;

and/or, the thickener comprises: at least one of hydroxyethyl cellulose and a polyurethane thickener;

and/or, the dispersant comprises: at least one of a sodium salt aqueous solution of a carboxylic acid polymer and an acrylic acid sodium salt dispersant;

and/or, the wetting agent is selected from a nonionic surfactant;

and/or, the defoamer is selected from: at least one of a modified silicone defoamer and a mineral oil defoamer;

and/or, the preservative is selected from: at least one of 5-chloro-2-methyl-4-isothiazolin-3-one, benzisothiazolin-3-one, 2-dibromo-3-cyanopropionamide;

and/or the pH regulator is selected from at least one of multifunctional pH regulator of silane organic silicon aqueous solution, multifunctional amine assistant, KOH and NaOH.

5. The antiviral, anti-formaldehyde coating of claim 4, wherein said wetting agent is selected from the group consisting of: at least one of DOW ECOSURF BD-109, Clariant GENANOL X080 and Clariant EMULSOGEN LCN 407;

and/or, the coalescent is selected from: at least one of OXEA OXFLIM 351CN, SH LOCA DA, SH LOCA A +, Chemoxy coast 290Plus, Eastman Optifilm Enhancer 300, RUNTAI RTC-290A;

and/or, the thickener is selected from: at least one of LOTTE HECELLOSETM B30K, LOTTE HECELLOSE B15K, Ashland Natrosol 250HBR, Shin-Etsu TyloseHS30000YP2, DOW ACRYSOL RM-3030, DOW ACRYSOL RM-725, DOW ACRYSOL RM-12W, BASF RHEOVIS PE1331, BASF RHEOVIS PU 1341;

and/or, the dispersant comprises: at least one of BASF DISPEX CX 4320, BASF DISpex AA4140AS, DOW OROTAN 731A, BASF SOKALAN PA 25X, NOPCO SN-5040;

and/or, the defoamer is selected from: at least one of BLACKBURN DISPELAIR CF 18441, BLACKBURN DISPELAIR CF 13635, BASF Foamastar ST 2410AC, NOPCO SN-DEFAOAMER 1340, and NOPCO NXZ;

and/or, the preservative is selected from: at least one of THOR ACTICIDE MBS, THOR ACTICIDE RS CONC, THOR ACTICIDE MBS5050, LONZA PROXEL 130S, LONZA PROXEL MB, VINK Vinkocide CMI 3.0;

and/or, the pH adjusting agent is selected from: WACKER SILRES BS 168, DOW APM-95, KOH, NaOH.

6. A method for preparing the antiviral and anti-formaldehyde coating as claimed in any one of claims 1 to 5, which comprises the steps of:

7. The method of preparing an antiviral and anti-formaldehyde coating according to claim 6, wherein the step of preparing the acrylate polymer having an anti-formaldehyde group and an antibacterial group comprises: mixing acrylamide, acrylic acid, hydroxyethyl methacrylate, butyl acrylate, an antibacterial component, an initiator, an emulsifier and a solvent, and then reacting to obtain the acrylate polymer containing the formaldehyde group and the antibacterial group.

8. The method of claim 7 wherein the emulsifier is selected from the group consisting of silicone emulsifiers;

and/or, the initiator is selected from t-butyl hydroperoxide;

and/or, the antimicrobial component comprises diamine silver hydroxide;

and/or, the solvent is selected from water;

and/or the mass ratio of the acrylamide, the acrylic acid, the hydroxyethyl methacrylate, the butyl acrylate, the emulsifier, the antibacterial component, the initiator and the solvent is (2-15): (8-12): (15-25): (15-20): (0.05-0.15): (0.3-0.8): (2-5): (45-50).

9. The method for preparing an antiviral and anti-formaldehyde coating according to any one of claims 6 to 8, wherein the step of mixing and dispersing comprises:

carrying out first mixing and dispersing treatment on water with the formula amount of 50-80%, the dispersing agent with the formula amount, the wetting agent with the formula amount and the defoaming agent with the formula amount of 30-50%;

adding the pigment with the formula amount and the filler with the formula amount for second mixing and dispersing treatment;

adding 25-40% of the thickener, 5-10% of water and the pH regulator according to the formula amount to perform third mixing and dispersing treatment;

adding the antiviral and anti-formaldehyde emulsion in a formula amount to perform fourth mixing and dispersing treatment;

and adding the balance of the defoaming agent, the balance of the film-forming assistant, the balance of the thickening agent, the balance of the freeze-thaw resistance stability, the balance of the preservative and the balance of water, and performing fifth mixing and dispersing treatment to obtain the antiviral and anti-formaldehyde coating.

10. The method for preparing an antiviral and anti-formaldehyde coating according to claim 9,

the conditions of the first mixed dispersion treatment include: under the condition that the rotating speed is 400-600 rpm, water, the dispersing agent, the wetting agent and the defoaming agent are added in sequence and dispersed for 2-3 minutes;

and/or the step of the second mixing and dispersing treatment comprises the following steps: adding the pigment and the filler under the condition that the rotating speed is 500-700 rpm, and performing dispersion treatment for 2-4 minutes;

and/or the step of the third mixing and dispersing treatment comprises the following steps: adding the thickening agent, the water and the pH regulator under the condition that the rotating speed is 1600-1800 rpm, and performing dispersion treatment for 20-30 minutes;

and/or the fourth mixing and dispersing treatment step comprises the following steps: adding the antiviral and anti-formaldehyde emulsion under the condition that the rotating speed is 800-900 rpm, and performing dispersion treatment for 2-4 minutes;

and/or the step of the fifth mixing and dispersing treatment comprises the following steps: and under the condition that the rotating speed is 800-900 rpm, sequentially adding the defoaming agent, the film-forming aid, the thickening agent, the freeze-thaw resistance stability, the preservative and the balance of water, and performing dispersion treatment for 10-15 minutes.