CN114149701B - Antiviral and formaldehyde-resistant A-grade fireproof interior wall coating and preparation method thereof - Google Patents

Antiviral and formaldehyde-resistant A-grade fireproof interior wall coating and preparation method thereof Download PDF

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CN114149701B
CN114149701B CN202111468061.7A CN202111468061A CN114149701B CN 114149701 B CN114149701 B CN 114149701B CN 202111468061 A CN202111468061 A CN 202111468061A CN 114149701 B CN114149701 B CN 114149701B
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shell powder
formaldehyde
antiviral
interior wall
calcined shell
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CN114149701A (en
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陈颖
区英强
蔡天康
刘伟达
陈文基
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Guangdong Carpoly Science & Technology Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

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Abstract

The invention discloses an antiviral and formaldehyde-resistant A-grade fireproof interior wall coating and a preparation method thereof, wherein the antiviral and formaldehyde-resistant A-grade fireproof interior wall coating comprises the following components in parts by weight: comprises 20 to 30 portions of deionized water, 0.3 to 0.6 portion of cellulose, 0.3 to 0.6 portion of dispersant, 0.3 to 0.8 portion of antifreeze, 30 to 45 portions of modified calcined shell powder slurry with the solid content of 65 to 75 percent, 5 to 10 portions of titanium pigment, 10 to 15 portions of photocatalyst dispersion liquid, 5 to 17 portions of heavy calcium carbonate, 5 to 9 portions of acrylic emulsion, 0.1 to 0.5 portion of defoamer and 0.3 to 0.8 portion of film forming additive; has good antiviral and antibacterial properties and formaldehyde resistance, excellent fireproof performance and storage stability, and is odorless and environment-friendly.

Description

Antiviral and formaldehyde-resistant A-grade fireproof interior wall coating and preparation method thereof
Technical Field
The invention relates to the field of interior wall coatings, in particular to an antiviral and formaldehyde-resistant A-grade fireproof coating and a preparation method thereof.
Background
Along with the increasing epidemic diseases, the public attention to bacteria and viruses is increased, the spread speed of the viruses is very high in public places such as schools, hospitals, markets, restaurants and the like with large flow of people, the viruses are easy to cross-infect, and in addition, a lot of viruses can survive for a long time without hosts, so that the virus protection challenge is raised, the traditional indoor decoration material basically has no antiviral function, and the interior wall coating occupying most of the indoor decoration area has great significance if the interior wall coating has the antiviral function.
Formaldehyde is determined as a carcinogen by the world health organization, and the influence of formaldehyde on human health is mainly reflected in abnormal smell, stimulation, allergy, abnormal lung function, abnormal liver function, abnormal immune function and the likeAnd (5) carrying out the following steps. When the indoor formaldehyde concentration reaches 0.1mg/m 3 In time, peculiar smell and uncomfortable feeling are generated; up to 0.5mg/m 3 It can stimulate eyes and cause lacrimation; up to 0.6mg/m 3 Throat discomfort or pain can result; higher concentrations can cause nausea, vomiting, cough, chest distress, asthma and even pulmonary edema. The national standard stipulates that the safety value of the formaldehyde concentration of indoor air is 0.1mg/m 3 The formaldehyde concentration of the newly-decorated house is generally 0.3-0.6mg/m 3 Therefore, the product with the formaldehyde removing function is selected to decorate the room, and great help is brought to purifying the formaldehyde in the room.
The conventional interior wall coating has high organic matter content and poor fireproof performance, can burn at high temperature, emits a lot of harmful gases and can accompany dense smoke, and in case of fire, the conventional interior wall coating causes great threat to escape of personnel. Provisions in "interior decoration design fire protection code for building" approved by the Ministry of housing and urban and rural construction: a class A fireproof material is adopted in places such as the interior decoration of a windowless room, the ceiling of an evacuation staircase, the front room, the wall surface, the ground and the like.
CN 104592841A discloses an inorganic antibacterial aldehyde-removing coating and a preparation method thereof, wherein inorganic nano zinc oxide is adopted as a main functional material for antibacterial aldehyde removal, and the nano zinc oxide can decompose cell walls of bacteria under the catalysis of visible light and remove formaldehyde through photocatalysis. On one hand, the nano zinc oxide can play a catalytic role only under the condition of a light source, and the effect is greatly reduced under the condition without the light source; on the other hand, the dosage of the emulsion is 20-30 parts, the content of organic matters is very high, the requirement of fire-proof grade cannot be met, and the emulsion does not belong to the category of inorganic coating.
CN 10449109A discloses an antiviral natural paint and a preparation method thereof, wherein antiviral agents are prepared by using honeysuckle, forsythia, radix isatidis, dandelion, houttuynia cordata and other Chinese herbal medicines, and the antiviral agents are added into a coating to prepare the antiviral natural paint. On the one hand, the anti-virus mechanism of these herbs in humans is not necessarily suitable for use in paints; on the other hand, the long-acting properties of antiviral agents are also a great challenge.
CN 111333862A discloses an antiviral emulsion composition, a coating and a preparation method thereof, wherein a water-based high polymer containing a high-content quaternary phosphonium salt unit is synthesized, and an inorganic metal nano composite material dispersion liquid is combined to prepare the antiviral emulsion composition. On one hand, the paint combines inorganic metal nano materials, and a plurality of metal ions have colors, so that the problem of color change of the paint is difficult to control while the antibacterial and antiviral properties of the paint are ensured; on the other hand, the coating prepared by the method does not have the functions of formaldehyde resistance and fire resistance.
The present invention also enumerates and contrasts some existing paint antiviral technologies, in combination with other data, summarized as follows: (1) The photocatalytic antibacterial antiviral material is prepared by reacting inorganic material with photocatalytic function with water or air under the action of light to generate superoxide radical O with high reactivity 2- And a reactive functional group such as hydroxyl radical OH, which reacts with microorganisms to produce CO 2 And H 2 O, thereby achieving the antibacterial and antiviral effects; (2) Metal and its derivatives, the metal dissolving mechanism, namely in the antibacterial, antiviral agent use process, inorganic metal ion in antibacterial, antiviral material dissolve gradually, react with protein, nucleic acid in vivo of microorganism, functional group (such as sulfydryl and amino) containing sulfur, ammonia, thus produce antibacterial, antiviral effect; (3) Natural antibiotic and antiviral materials, including plant sources and animal sources, mainly comprising alkaloid, organic acid, phenols and volatile oil or macromolecular protein and polysaccharide, wherein the molecules of the materials contain S (= O) -S-bonds, which play a role in sulfur-containing substances in microbial cells, can inhibit and control the normal metabolism of thalli, thereby playing a role in sterilization; (4) Organic low-molecular antibacterial and antiviral materials, including quaternary ammonium salts, quaternary phosphonium salts, biguanides, alcohols, phenols, organic metals, pyridines, imidazoles and the like, wherein the antibacterial and antiviral mechanisms are mainly combined with anions on the surfaces of cell membranes of bacteria and molds or react with sulfydryl to destroy the synthetic system of proteins and the cell membranes, thereby inhibiting the propagation of the bacteria and the molds; (5) The organic high molecular antibacterial and antiviral material is obtained by introducing antibacterial and antiviral functional groups, wherein the antibacterial and antiviral functional groups can be introduced by homopolymerization or copolymerization of functional group monomers or by graftingOr grafting a metal precursor into the structure of the emulsion or resin.
However, different routes to antiviral technologies also present different problems, such as: photocatalysts, which must rely on light sources to function; metals and derivatives thereof can bring serious color change to the paint and also bring great challenges to the stability of the paint; natural antibacterial and antiviral materials, the extraction process is complex and the extraction efficiency is not high; the organic low-molecular antibacterial and antiviral material is easy to migrate to the surface of a paint film, and the long-acting property is insufficient; many organic polymer antibacterial and antiviral materials are not resistant to high temperature, and the stability of emulsion or resin and the compatibility of the emulsion or resin with a system when the emulsion or resin is applied to a coating are not good.
In the aspect of formaldehyde resistance of the coating, a plurality of reports are also provided at present, and the formaldehyde-resistant interior wall coating can be developed through different technical routes, mainly comprising 3 types, namely, formaldehyde-resistant emulsion, photocatalyst photocatalytic material and other functional powder for adsorbing and decomposing formaldehyde.
CN 112521777A discloses an inorganic mineral shell powder coating with formaldehyde purification and decomposition functions, which utilizes the combination of a nano catalyst and shell powder to enable the shell powder to decompose formaldehyde into CO 2 And H 2 And O. However, the shell powder mainly contains calcium carbonate, has limited formaldehyde decomposition capability, and mainly contains Ca (OH) after sintering and curing 2 ,Ca 2+ Very readily with SiO 3 2- Reaction, resulting in a thick lump after the system.
Different formaldehyde-resistant technical routes also have respective problems, and by utilizing the acrylic emulsion, a plurality of organic matters are added, so that the fireproof performance of the product is poor; the photocatalyst catalytic material has the effect of resisting formaldehyde only under the condition of wide sources; the powder with other functions of adsorption and decomposition is added, a lot of powder only has the adsorption function and is released very subsequently, and the compatibility of the powder with the function of formaldehyde decomposition and a system is not good, so that the storage stability of the product is not good easily.
In the aspect of fireproof interior wall coatings, many interior wall inorganic coatings can meet the A-level fireproof requirement at present, but need to simultaneously achieve the A-level fireproof, antiviral and formaldehyde purification functions, and reports are not yet found at present, so that the development of an interior wall product with the fireproof performance, formaldehyde purification function and antiviral function is urgently needed.
Disclosure of Invention
Aiming at the problem of single function of the existing interior wall coating, the invention provides the anti-virus anti-formaldehyde A-level fireproof interior wall coating on the one hand, and the alkali-rich performance of the modified calcined shell powder is utilized to ensure that a paint film can keep high alkalinity for a long time and inhibit microorganisms such as bacteria, mildew, viruses and the like from propagating and growing on the surface of the paint film so as to achieve the functions of resisting bacteria and viruses; the photocatalyst dispersion liquid and the acrylic emulsion are compounded, so that a paint film can continuously degrade formaldehyde in the presence or absence of a light source, the content of organic matters is reduced, and the modified calcined shell powder is used as a main film forming substance, so that the content of the organic matters in the whole paint is very low, and the A-level fireproof standard is reached.
The invention also provides a preparation method of the antiviral and formaldehyde-resistant A-grade fireproof coating, which is simple to operate, easy to control the process and stable in performance of the obtained coating.
In order to realize the purpose, the technical scheme of the invention is as follows:
an antiviral and formaldehyde-resistant A-grade fireproof interior wall coating comprises the following components in parts by weight: comprises 20-30 parts of deionized water, 0.3-0.6 part of cellulose, 0.3-0.6 part of dispersing agent, 0.3-0.8 part of antifreeze, 30-45 parts of modified calcined shell powder slurry with the solid content of 65-75%, 5-10 parts of titanium dioxide, 10-15 parts of photocatalyst dispersion liquid, 5-17 parts of triple superphosphate, 5-9 parts of acrylic emulsion, 0.1-0.5 part of defoaming agent and 0.3-0.8 part of film forming auxiliary agent.
In the invention, the modified calcined shell powder slurry is prepared by the following method: carrying out surface coating treatment on the calcined shell powder by using a titanate coupling agent, and then carrying out emulsification treatment by using a surfactant for emulsifying the calcined shell powder; specifically, the following may be mentioned:
preparing calcined shell powder: calcining shell powder at 1000-1200 ℃, cooling after calcining completely, and then carrying out ball milling by using a ball mill;
aging of calcined shell powder: soaking calcined shell powder in deionized water for curing;
preparing an emulsion: mixing deionized water and a surfactant for emulsifying and calcining the shell powder, heating to 50-60 ℃, stirring for 58-62min, and keeping the system in a uniform state for later use;
surface modification calcined shell powder slurry: mixing deionized water and a titanate coupling agent, uniformly stirring, adding cured calcined shell powder, dispersing, coating the surface of the calcined shell powder, adding an emulsion for emulsification treatment, and passing through a 160-mesh filter cloth after dispersing to obtain the modified calcined shell powder slurry.
The calcined shell powder has high alkalinity and large surface energy, and is easily unstable when directly added into a coating system, and the method is mainly shown in the following aspects: 1. the calcined shell powder has high thixotropy and is difficult to disperse in the coating; 2. calcining the shell powder can rob an emulsifier on the surface of the latex particles, so that emulsion breaking is easily caused, and the whole system is damaged; 3. bare calcined shell powder vs. Mg 2+ 、SiO 3 2- 、Al 3+ Are sensitive and can react to cause flocculation and caking; the calcined shell powder is prepared by the following method: carrying out surface coating treatment on the calcined shell powder by using a titanate coupling agent, and then carrying out emulsification treatment by using a surfactant; the method does not destroy the alkali-rich property of calcined shell powder, and can reduce OH when added into water - The burst release of the surfactant reduces the direct impact on the emulsion, the coating of the surfactant can reduce the surface tension, improve the dispersibility, and increase the compatibility with other components and the long-term storage stability; the obtained modified calcined shell powder slurry has high strength porous structure and good water respiration function, and the main component of the modified calcined shell powder slurry is calcium hydroxide which is used as a main film forming substance and absorbs CO in the air 2 And calcium carbonate is generated through reaction, the calcium carbonate is solidified to form a film, and after the film is formed, the pH value of the paint film can be ensured to be 11.5-12.5, and microorganisms such as bacteria, mould, viruses and the like can not be propagated and grown on the surface of the paint film, so that the paint film has good antibacterial and antiviral functions.
In the invention, the acrylic emulsion is prepared by the following method:
pre-emulsifying monomers: sequentially adding a hard monomer, a soft monomer, a functional monomer and an emulsifier into deionized water, heating to 73-75 ℃, and fully stirring to prepare a pre-emulsified monomer;
synthesizing a seed emulsion: mixing deionized water and 1/4 pre-emulsified monomer, heating to 78-80 ℃, adding 1/4 initiator, and initiating polymerization to obtain seed emulsion;
heating the seed emulsion to 81-83 ℃, uniformly dropwise adding 2/4 pre-emulsified monomers and 2/4 initiators into the seed emulsion at 81-83 ℃ within 3-3.5h, and mixing for polymerization;
heating to 85 ℃, dripping 1/4 of the remaining pre-emulsified monomer and 1/4 of the remaining initiator into the mixture within 1 hour, and preserving heat for 0.5 to 1 hour after the dripping is finished;
cooling to 63-65 deg.C, adding tert-butyl hydroperoxide and NaHSO 3 Reducing the content of residual monomers, after 0.5-1h, reducing the temperature to 35-40 ℃, adjusting the PH to 7.5-8 by ammonia water, and filtering to obtain the acrylic emulsion.
Further, the functional monomer used in the process of preparing the acrylic emulsion is one of acetoacetoxy ethyl methacrylate (AAEMA), acrylamide or methacrylamide, preferably acetoacetoxy ethyl methacrylate (AAEMA).
In the invention, the photocatalyst dispersion liquid is prepared by the following method:
in deionized water, the photocatalyst is prepared by pre-dispersing with at least one nonionic surfactant, and the solid content in the photocatalyst dispersion liquid is more than 40%.
The photocatalyst dispersion liquid and the acrylic emulsion are compounded, the photocatalyst dispersion liquid decomposes formaldehyde under the condition of light, the acrylic emulsion can decompose formaldehyde under the conditions of light and no light, and the acrylic emulsion is an organic matter, so that the addition of the photocatalyst dispersion liquid can reduce the use amount of the acrylic emulsion and reduce the fire resistance to reach level A, and the compounding of the photocatalyst dispersion liquid and the acrylic emulsion are adopted and are mutually cooperated to mutually make up for the defects; and the alkali-rich performance of the modified calcined shell powder slurry can also stimulate the reducibility of formaldehyde, so that the formaldehyde is easier to be oxidized, and the modified calcined shell powder slurry, the photocatalyst dispersion liquid and the acrylic emulsion have a synergistic effect with each other, thereby achieving the A-grade fire prevention and simultaneously decomposing the formaldehyde under the condition of light or no light, and meeting the requirement of removing the formaldehyde.
In the invention, the surfactant used in the modification process of the calcined shell powder is sodium dodecyl sulfate or polyoxyethylene ether.
In the invention, the rutile titanium dioxide which is prepared by a chlorination method and is not subjected to surface coating is selected, has good compatibility with the modified calcined shell powder, and is favorable for the long-term storage stability of the coating.
In the invention, the cellulose is selected from hydroxyethyl cellulose and/or hydroxypropyl methyl cellulose, preferably hydroxyethyl cellulose.
In the invention, the dispersant is sodium polyacrylate dispersant.
In the invention, the antifreezing agent is one of ethylene glycol, propylene glycol and surfactant type antifreezing agent, and propylene glycol is preferred.
In the invention, the defoaming agent is one or more of mineral oil, vegetable oil, polyether modified organic silicon and hydrocarbon, and strong hydrophobic mineral oil is preferred.
In the invention, the film-forming auxiliary agent is selected from alcohol ether and/or alcohol ester film-forming auxiliary agents, preferably alcohol ester film-forming auxiliary agents, and more preferably Iseman OE300.
In the invention, the heavy calcium is selected as high as possible in purity, and Mg brought by impurities is selected as much as possible 2+ 、Al 3+ It has a slight effect on the long-term stability of the system, preferably 1250 mesh.
A preparation method of an antiviral and formaldehyde-resistant A-grade fireproof interior wall coating comprises the following steps:
mixing deionized water and cellulose, fully stirring and dispersing, then adding a dispersing agent and an antifreezing agent, and uniformly stirring to obtain a mixed solution 1;
adding the modified calcined shell powder slurry, the titanium dioxide, the photocatalyst dispersion liquid and the heavy calcium into the mixed solution 1 in sequence, and dispersing until the fineness is less than 60um to obtain a mixed solution 2;
and (3) adding the acrylic emulsion, the defoaming agent and the film forming auxiliary agent into the mixed solution 2 in sequence, and stirring uniformly.
The invention has the beneficial effects that:
1. and (3) antibacterial and antiviral: the high alkalinity of the calcined shell powder is utilized to maintain the system in an alkali-rich state, and the porous structure of the calcined shell powder can ensure that the pH value of a paint film is 11.5-12.5 for a long time, microorganisms such as bacteria, molds, viruses and the like can not propagate and grow on the surface of the paint film, and the synergistic effect of the two functions is realized by the catalytic decomposition function of the photocatalyst, so that the paint film is further ensured to have good antibacterial and antiviral functions.
2. Formaldehyde decomposition: the photocatalyst can generate a photocatalytic reaction similar to photosynthesis under the irradiation of light to generate free hydroxyl and active oxygen with extremely strong oxidizing power, has a very strong photooxidation function, can oxidize and decompose formaldehyde, and has a very strong purification function on the formaldehyde; the acrylic emulsion can also purify formaldehyde under the condition of no light source; the alkali-rich environment of the paint film can also excite the reducibility of formaldehyde, so that the formaldehyde is easier to be oxidized; three different technical paths and mutual cooperation can ensure that the paint film has extremely high decomposition function on formaldehyde no matter whether under the condition of having a light source or not.
3.A grade fire protection: except a small amount of emulsion and a very small amount of organic auxiliary agent, other components in the paint are inorganic materials, the proportion of organic components is less than 5wt%, the fire-proof grade reaches A level, and the formed paint film has good incombustibility and fire resistance and good fire-proof effect.
4. And (3) smell removal and environmental protection: because calcined shell powder is mainly used as a film forming substance, the addition amount of the emulsion is small, volatile Organic Compounds (VOC) brought into the coating are few, the coating does not need to be added with a preservative, formaldehyde and other harmful components are not contained, and the environment-friendly performance of the coating is high.
5. The storage stability is high: the calcined shell powder is subjected to surface treatment to prepare slurry, so that the compatibility with other components is greatly increased, and particularly the direct impact on the emulsion is reduced; the pre-emulsification of the photocatalyst inhibits the self-aggregation of the photocatalyst, and reduces the thickening tendency of the system; functional monomers are introduced in the process of preparing the acrylic emulsion, and a designed synthesis process is combined, so that the formaldehyde resistance function is ensured, the alkali resistance is good, the acrylic emulsion has good compatibility with other components of a system, several important links influencing the stability are optimized, and the final coating has good storage stability.
Detailed Description
The modified calcined shell slurries used in the following examples or comparative examples were prepared by the following steps:
s1: preparing calcined shell powder: fully calcining shell powder at 1000-1200 ℃, cooling after calcining, and then carrying out ball milling by using a ball mill;
s2: aging of calcined shell powder: soaking the calcined shell powder obtained in the step S1 in deionized water, and fully curing;
s3: preparing an emulsion: adding deionized water and sodium dodecyl sulfate into a heating container according to a mass ratio of 99;
s4: modified calcined shell powder slurry: and (2) adding deionized water and a titanate coupling agent into a stirring kettle, uniformly stirring, adding the calcined shell powder aged in the step (S2), fully dispersing, coating the surface of the calcined shell powder, adding the emulsion in the step (S3), emulsifying the calcined shell powder coated by the coupling agent, fully dispersing, and then filtering through a 160-mesh filter cloth to obtain the modified calcined shell powder slurry.
The acrylic emulsions used in the following examples or comparative examples were prepared by the following steps:
s1, pre-emulsifying monomers, namely adding deionized water into a reaction kettle, then sequentially adding a hard monomer, a soft monomer, acetoacetoxy ethyl methacrylate and an emulsifier, heating to 75 ℃, and fully stirring to prepare pre-emulsifying monomers;
s2, synthesizing seed emulsion, namely adding deionized water and 1/4 pre-emulsified monomers into a reaction kettle, heating to 78 ℃, adding 1/4 initiator, initiating polymerization, and synthesizing seed emulsion;
s3, heating to 83 ℃, uniformly dripping 2/4 of pre-emulsified monomer and 2/4 of initiator into the reaction kettle within 3-3.5h, and fully polymerizing;
s4, heating to 85 ℃, dropwise adding the remaining 1/4 pre-emulsified monomer and 1/4 initiator into the reaction kettle within 1h, and preserving heat for 0.5h after dropwise adding;
s5, cooling to 65 ℃, and using tert-butyl hydroperoxide (TBHP) and NaHSO 3 Reducing the content of residual monomers, after 0.5h, reducing the temperature to 40 ℃, adjusting the PH value to 7.5-8 by ammonia water, filtering and discharging.
The photocatalyst dispersion used in each of the following examples or comparative examples was prepared by the following steps:
adding a certain amount of deionized water into a reaction kettle, adding a nonionic surfactant, uniformly stirring, adding a photocatalyst, dispersing at a high speed until the fineness is less than 60um.
The solvent used in each of the following examples or comparative examples was deionized water.
Example 1
The antiviral and formaldehyde-resistant class A fireproof interior wall coating comprises the raw materials shown in the table 1.
TABLE 1
Figure BDA0003392359170000101
Figure BDA0003392359170000111
The preparation method of the antiviral formaldehyde-resistant A-grade fireproof interior wall coating comprises the following steps:
s1, adding water and cellulose in the table 1 into a stirring kettle, fully stirring and dispersing, then adding a dispersing agent and an antifreezing agent, and uniformly stirring;
s2, sequentially adding the modified calcined shell powder slurry, the titanium dioxide, the photocatalyst dispersion liquid and the coarse whiting in the table 1 into a reaction kettle, and dispersing at a high speed until the fineness is less than 60um;
and S3, sequentially adding the acrylic emulsion, the defoaming agent and the film forming auxiliary agent in the table 1 into the reaction kettle, and uniformly stirring at a medium speed to obtain a finished product.
Example 2
The antiviral and formaldehyde-resistant class A fireproof interior wall coating comprises the raw materials shown in the table 2.
TABLE 2
Figure BDA0003392359170000121
The preparation method of the antiviral formaldehyde-resistant A-grade fireproof interior wall coating comprises the following steps:
s1, adding water and cellulose in the table 2 into a stirring kettle, fully stirring and dispersing, then adding a dispersing agent and an antifreezing agent, and uniformly stirring;
s2, sequentially adding the modified calcined shell powder slurry, the titanium dioxide, the photocatalyst dispersion liquid and the coarse whiting in the table 2 into a reaction kettle, and dispersing at a high speed until the fineness is less than 60um;
and S3, sequentially adding the acrylic emulsion, the defoaming agent and the film forming auxiliary agent in the table 2 into the reaction kettle, and uniformly stirring at a medium speed to obtain a finished product.
Example 3
The antiviral and formaldehyde-resistant class A fireproof interior wall coating comprises the raw materials shown in the table 3.
TABLE 3
Figure BDA0003392359170000131
The preparation method of the antiviral formaldehyde-resistant A-grade fireproof interior wall coating comprises the following steps:
s1, adding water and cellulose in the table 3 into a stirring kettle, fully stirring and dispersing, then adding a dispersing agent and an antifreezing agent, and uniformly stirring;
s2, sequentially adding the modified calcined shell powder slurry, the titanium dioxide, the photocatalyst dispersion liquid and the coarse whiting in the table 3 into a reaction kettle, and dispersing at a high speed until the fineness is less than 60um;
and S3, sequentially adding the acrylic emulsion, the defoaming agent and the film forming auxiliary agent in the table 3 into the reaction kettle, and uniformly stirring at a medium speed to obtain a finished product.
Comparative example 1
Compared with the embodiment 1, the modified calcined shell powder slurry is lacked, and other raw materials are unchanged; and adding no modified calcined shell powder slurry in the preparation process to obtain the product.
Comparative example 2
Compared with the embodiment 1, the modified calcined shell powder slurry is lacked, the acrylic emulsion is changed into the common styrene-acrylic emulsion, and other raw materials are unchanged; the modified calcined shell powder slurry and the acrylic emulsion are not added in the preparation process, so that the product is obtained.
Comparative example 3
Compared with the example 1, the comparative example lacks acrylic emulsion and has the same raw materials; the product is obtained without adding acrylic emulsion in the preparation process.
Comparative example 4
Compared with the example 1, the comparative example lacks photocatalyst dispersion liquid, and other raw materials are unchanged; the photocatalyst dispersion liquid is not added in the preparation process to obtain the product.
Comparative example 5
Compared with the example 1, the comparative example lacks photocatalyst dispersion liquid and acrylic emulsion, and other raw materials are unchanged; the photocatalyst dispersion liquid and the acrylic emulsion are not added in the preparation process, and the product is obtained.
The antiviral performance and antiviral durability were tested according to T/CNCIA 01014-2020 "antibacterial and antiviral paint".
The antibacterial performance is tested according to HG-T3950-2007 antibacterial paint.
The formaldehyde purification performance and formaldehyde purification durability were tested according to JCT 1074-2008 "indoor air purification function coating material purification performance".
Fire ratings are classified according to GB 8624-2012 "fire ratings for building materials and products".
The VOC of the product is tested according to GB 18582-2020 Limited amount of harmful substances in wall paint for buildings.
The products obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to corresponding performance tests according to the above criteria, and the results are shown in Table 4.
TABLE 4
Figure BDA0003392359170000151
As is clear from Table 4, the products prepared in examples 1 to 3 are excellent in antiviral and antibacterial properties and also in durability, formaldehyde resistance and durability, and fire resistance, and have few volatile organic compounds; compared with the comparative example 1, the modified calcined shell powder slurry is lacked, the antiviral and antibacterial functions are basically absent, and the formaldehyde purification performance is slightly reduced; compared with the comparative example 2, the modified calcined shell powder slurry is lacked, the common acrylic emulsion is adopted, the antiviral and antibacterial functions are obviously reduced, the antiviral and antibacterial functions are basically not generated, and the formaldehyde purification performance is also reduced more; compared with the comparative example 3, the acrylic emulsion is lacked, the antiviral and antibacterial functions are not obviously reduced, and the formaldehyde purification performance is reduced to a certain extent; compared with the comparative example 4, the example 1 lacks of photocatalyst dispersion liquid, the antiviral and antibacterial properties are not obviously reduced, and the formaldehyde purification performance is obviously reduced; compared with the comparative example 5, the example 1 lacks of photocatalyst dispersion liquid and acrylic emulsion, has no obvious reduction of antiviral and antibacterial properties, and has weak formaldehyde purification performance.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. An antiviral and formaldehyde-resistant A-grade fireproof interior wall coating is characterized by comprising the following components in parts by weight: comprises 20 to 30 portions of deionized water, 0.3 to 0.6 portion of cellulose, 0.3 to 0.6 portion of dispersant, 0.3 to 0.8 portion of antifreeze, 30 to 45 portions of modified calcined shell powder slurry with the solid content of 65 to 75 percent, 5 to 10 portions of titanium pigment, 10 to 15 portions of photocatalyst dispersion liquid, 5 to 17 portions of heavy calcium carbonate, 5 to 9 portions of acrylic emulsion, 0.1 to 0.5 portion of defoamer and 0.3 to 0.8 portion of film forming additive;
the modified calcined shell powder slurry is prepared by the following method:
and (3) carrying out surface coating treatment on the calcined shell powder by using a titanate coupling agent, and then carrying out emulsification treatment by using a surfactant for emulsifying the calcined shell powder.
2. The antiviral and formaldehyde-resistant class A fireproof interior wall coating according to claim 1, wherein the modified calcined shell powder slurry is prepared by the following method:
preparing calcined shell powder: calcining shell powder at 1000-1200 ℃, cooling after calcining completely, and then carrying out ball milling by using a ball mill;
aging of calcined shell powder: soaking calcined shell powder in deionized water for curing;
preparing an emulsion: mixing deionized water and a surfactant for emulsifying and calcining the shell powder, heating to 50-60 ℃, stirring for 58-62min, and keeping the system in a uniform state for later use;
surface modification calcined shell powder slurry: mixing deionized water and a titanate coupling agent, uniformly stirring, adding cured calcined shell powder, dispersing, coating the surface of the calcined shell powder, adding an emulsion for emulsification treatment, and passing through 160-mesh filter cloth after dispersing to obtain the modified calcined shell powder slurry.
3. The antiviral and formaldehyde-resistant class A fire-retardant interior wall coating according to claim 1, wherein the acrylic emulsion is prepared by the following method:
pre-emulsifying monomers: sequentially adding a hard monomer, a soft monomer, a functional monomer and an emulsifier into deionized water, heating to 73-75 ℃, and fully stirring to prepare a pre-emulsified monomer;
synthesizing a seed emulsion: mixing deionized water and 1/4 pre-emulsified monomer, heating to 78-80 ℃, adding 1/4 initiator, and initiating polymerization to obtain seed emulsion;
heating the seed emulsion to 81-83 ℃, uniformly dropwise adding 2/4 pre-emulsified monomers and 2/4 initiators into the seed emulsion at 81-83 ℃ within 3-3.5h, and mixing for polymerization;
heating to 85 ℃, dripping 1/4 of the remaining pre-emulsified monomer and 1/4 of the remaining initiator into the mixture within 1 hour, and preserving heat for 0.5 to 1 hour after the dripping is finished;
cooling to 63-65 deg.C, and mixing with tert-butyl hydroperoxide and NaHSO 3 Reduction of residual monomer contentAfter 0.5-1h, the temperature is reduced to 35-40 ℃, the pH is adjusted to 7.5-8 by ammonia water, and the acrylic emulsion is obtained by filtration.
4. The antiviral and anti-formaldehyde class-A fireproof interior wall coating according to claim 1, wherein the photocatalyst dispersion is prepared by the following method:
in deionized water, at least one nonionic surfactant is used for pre-dispersion, and the solid content in the photocatalyst dispersion liquid is more than 40%.
5. The antiviral formaldehyde-resistant class A fireproof interior wall coating according to claim 1, wherein the titanium dioxide is rutile titanium dioxide which is prepared by a chlorination method and is not subjected to surface coating; the surfactant for emulsifying the shell powder is sodium dodecyl sulfate or polyoxyethylene ether; the cellulose is hydroxyethyl cellulose and/or hydroxypropyl methyl cellulose; the dispersant is polyacrylic acid sodium salt dispersant.
6. The antiviral and formaldehyde-resistant class A fireproof interior wall coating according to claim 1, wherein the antifreeze agent is one selected from ethylene glycol, propylene glycol and surfactant type antifreeze agents.
7. The antiviral and formaldehyde-resistant class A fireproof interior wall coating according to claim 1, wherein the defoamer is selected from one or more of mineral oil, vegetable oil, polyether modified silicone and hydrocarbon.
8. The antiviral and formaldehyde-resistant class A fireproof interior wall coating according to claim 1, wherein the film forming aid is selected from alcohol ether and/or alcohol ester film forming aids.
9. A method for preparing the antiviral and formaldehyde-resistant class a fire-retardant interior wall coating according to any one of claims 1 to 8, comprising the steps of:
mixing deionized water and cellulose, fully stirring and dispersing, then adding a dispersing agent and an antifreezing agent, and uniformly stirring to obtain a mixed solution 1;
adding the modified calcined shell powder slurry, the titanium dioxide, the photocatalyst dispersion liquid and the heavy calcium into the mixed solution 1 in sequence, and dispersing until the fineness is less than 60um to obtain a mixed solution 2;
and (3) adding the acrylic emulsion, the defoaming agent and the film forming auxiliary agent into the mixed solution 2 in sequence, and stirring uniformly.
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