Environment-friendly water-based interior wall coating with ceramic glaze effect and preparation method thereof

Abstract

This invention provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. Based on the total mass of the interior wall coating, the water-based interior wall coating comprises the following components in the following mass percentages: silicone oil-modified acrylic polyurethane copolymer emulsion: 10.0-20.0 wt%; cross-linked nano-inorganic dispersion: 10.0-16.0 wt%; glaze gloss adjusting powder: 1.0-5.0%; pigments and fillers: 30.0-40.0 wt%; cellulose: 0.3-0.5 wt%; hydrophobic agent: 0.5-2.0 wt%; organosilicon additive: 0.5%-1.5%; other additives: 2.5-4.5 wt%; the other additives include at least one selected from wetting agents, dispersants, defoamers, pH adjusters, bactericides and fungicides, film-forming aids, and antifreeze agents; and water: 15.0-35.0 wt%. In the formulation of the water-based interior wall coating, a dense three-dimensional spatial structure of organic polymer-inorganic filler is formed by cross-linking silicone oil-modified acrylic polyurethane copolymer emulsion with silica nanoparticles. This gives the water-based interior wall coating scratch resistance and hydrophobic properties, and, in conjunction with other formulation components, further improves the hardness, abrasion resistance, stain resistance, and environmental performance of the water-based interior wall coating. The hardness of the interior wall coating is H grade, the abrasion resistance is no more than 12, and the stain resistance is I grade.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, and more specifically relates to an environmentally friendly water-based interior wall coating with ceramic glaze effect and its preparation method. Background Technology

[0002] In the process of economic and social development, consumers have increasingly higher requirements for interior decoration materials, demanding new standards not only in terms of appearance, odor, functionality, and environmental friendliness. For special environments such as hospitals, public spaces, operating rooms, and laboratories, where the performance requirements for wall coatings are even higher, wall coatings with high hardness, scratch resistance, stain resistance, easy cleaning, and certain fire resistance properties are becoming increasingly popular among consumers.

[0003] CN109626868A discloses a porcelain-like coating and flexible stone-like facing bricks, comprising the following raw materials in parts: 15-40 parts nano-silicon carbide, 20-35 parts calcium carbonate, 8-12 parts loess powder, 10-15 parts sodium oxalate, 0.5-2 parts hydroxyethyl methyl cellulose, 1-3 parts organic bentonite, 3-7 parts binder, and 20-30 parts pure water. This technology improves the stain resistance of the porcelain-like coating after solidification by adding nano-silicon carbide, calcium carbonate, and loess powder, making the flexible stone-like facing bricks made with this coating less susceptible to contamination. The porcelain-like and glaze-like effect mainly comes from the high-hardness and high-wear-resistant nano-silicon carbide. The film-forming substance is ordinary acrylic emulsion, and the film has a certain degree of hardness, wear resistance, and glaze-like effect after formation. This type of product uses a low amount of film-forming substance, only 3-7%, resulting in a low pigment volume concentration (PVC) and poor stain and dirt resistance. Furthermore, nano-silicon carbide is expensive, limiting its widespread application. Additionally, the coating has a high viscosity, making it suitable only for trowel application and not for roller or spray application, resulting in low application efficiency.

[0004] CN108864831A discloses a water-based environmentally friendly imitation porcelain coating and its construction method, including a water-based plastic primer, a water-based acrylic ceramic intermediate coat, and a water-based UV topcoat. The water-based plastic primer includes 31-59 parts of water-based acrylic modified chlorinated polypropylene resin, 6-20 parts of deionized water, 2-10 parts of calcium powder, 3-10 parts of mica powder, and 2-10 parts of water-based additives. The water-based acrylic ceramic intermediate coat includes 50-70 parts of silicone modified acrylic emulsion, 12-19 parts of ceramic powder, 0-3 parts of titanium dioxide, 16-20 parts of deionized water, 10-20 parts of color paste, and 2-7 parts of water-based additives. The water-based UV topcoat includes 40-70 parts of water-based UV curing resin, 20-30 parts of reactive diluent, 10-25 parts of deionized water, 3-6 parts of photoinitiator, and 0.2-1 parts of water-based additives. Among them, the water-based acrylic ceramic intermediate coat serves as the supporting component of the imitation porcelain coating system, providing a certain degree of hardness support to the paint film system. The water-based UV topcoat is one or a mixture of fluorinated acrylic resin or polyurethane acrylate, providing the coating system with a certain degree of stain resistance and anti-fouling properties. The entire coating system has a certain imitation porcelain and glaze effect. However, the construction process of this type of product is relatively complex, requiring three coats, resulting in high costs. Furthermore, the water-based UV topcoat is relatively thin, serving only as a topcoat to adjust gloss and provide stain resistance and easy cleaning, and is easily damaged under external forces.

[0005] CN108219666A discloses an infrared-resistant, antibacterial, and weather-resistant water-based imitation porcelain coating and its preparation method. The water-based imitation porcelain coating comprises the following raw materials in parts by weight: modified polyimide resin solution, lime powder, calcite powder, titanium dioxide, bentonite, aerogel heat insulation particles, nano-alumina 0.6-2 parts, water-based defoamer 0.2-0.6 parts, alkali-swellable thickener 0.1-0.3 parts, and water 60-100 parts. The preparation method includes the preparation of modified polyimide resin solution, mixing, and defoaming. The process involves uniformly mixing lime powder, calcite powder, titanium dioxide, bentonite, aerogel insulating particles, nano-alumina, monochlorotrifluorosuccinic acid, n-butyl acetoacetate, and 4-hydroxyphenylethylamine to obtain component A. Modified polyimide resin solution and an alkali-swellable thickener are then uniformly mixed to obtain component B. Components A and B are mixed, heated to 35-50℃, and stirred at 200-400 rpm for 20 minutes. Water is then added, and the mixture is stirred and kept at the temperature for another 30 minutes to obtain a final mixture. After cooling to room temperature, a water-based defoamer is added, and the mixture is stirred until uniformly dispersed and free of particulate matter, resulting in an infrared-resistant, antibacterial, and weather-resistant water-based imitation porcelain coating. However, the production process of this water-based imitation porcelain coating is complex, and the modified polyimide resin contains formaldehyde, making it unsuitable for use as an environmentally friendly interior wall coating.

[0006] CN105778632A discloses a water-resistant, odor-neutralizing water-based imitation porcelain coating. The components and mass percentages of each raw material are as follows: calcite powder 10-20%, double-flying powder 10-20%, calcium carbonate 8-12%, Bletilla striata powder 2-4%, corn starch 1-3%, carboxymethyl cellulose 0.5-1.5%, phenolic resin 0.5-1.5%, glutaraldehyde 0.5-1.5%, air purification particles 1-3%, and water 25-55%. The proposed formula is comprehensive and rationally formulated, using green, natural, and environmentally friendly raw materials. However, the phenolic resin used is sensitive to ultraviolet light, exhibiting poor weather resistance and heat resistance; the formula has a high PVC content, resulting in poor stain resistance; the production process is complex, requiring heating of the materials to ensure the release of the colloidal substances in the Bletilla striata powder and corn starch as film-forming substances in the coating, leading to poor weather resistance.

[0007] In summary, existing imitation porcelain coatings generally suffer from poor stain resistance, high cost, and complex production and application processes due to limitations in their formulation. Therefore, providing an interior wall coating that offers superior scratch resistance, stain resistance, easy cleaning, and environmental friendliness, while also having a simple and easy preparation and application process, is a pressing issue that needs to be addressed. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. In the formulation of this water-based interior wall coating, a dense three-dimensional organic polymer-inorganic filler structure is formed by cross-linking a silicone oil-modified acrylic polyurethane copolymer emulsion with silica nanoparticles. This imparts scratch resistance and hydrophobicity to the water-based interior wall coating, and, in conjunction with other formulation components, further enhances its hardness, abrasion resistance, stain resistance, and environmental performance. This solves the problems of existing imitation porcelain coatings, such as poor stain resistance, high cost, and complex production and application processes.

[0009] The technical solution of the present invention is as follows:

[0010] This invention provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. Based on the total mass of the interior wall coating, the water-based interior wall coating comprises the following components by mass percentage:

[0011] Silicone oil modified acrylic polyurethane copolymer emulsion: 10.0-20.0 wt%;

[0012] Cross-linked nano-inorganic dispersions: 10.0-16.0 wt%;

[0013] Glaze gloss adjusting powder: 1.0-5.0%;

[0014] Pigments and fillers: 30.0-40.0 wt%;

[0015] Cellulose: 0.3-0.5 wt%;

[0016] Hydrophobic agent: 0.5-2.0 wt%;

[0017] Organosilicon additives: 0.5%-1.5%;

[0018] Other additives: 2.5-4.5 wt%;

[0019] The other additives include at least one of wetting agents, dispersants, defoamers, pH adjusters, bactericides and fungicides, film-forming aids, and antifreeze agents; and

[0020] Water: 15.0-35.0wt%;

[0021] The interior wall coating has a hardness of H grade, an abrasion resistance of no more than 12, and a stain resistance of I grade.

[0022] Furthermore, the polymer side chains of the silicone oil modified acrylic polyurethane copolymer emulsion have a 7-8% grafting rate of silicone oil groups.

[0023] Furthermore, the weight-average molecular weight of the silicone oil-modified acrylic polyurethane copolymer emulsion is 90,000-140,000, and the molecular weight distribution Mw / Mn is approximately 2-4.

[0024] Furthermore, the preparation method of the silicone oil-modified acrylic polyurethane copolymer emulsion includes:

[0025] Step R1: Mix acrylic polyol monomer (AP) with single-terminated silicone oil (M), purge with nitrogen, preheat to 50-70℃, and continue to raise the temperature to 85-105℃ within 0.3-1h, so that the reaction can proceed at this temperature and continue for 4-6 hours. The carbon double bond of the acrylic polyol monomer undergoes a bulk polymerization reaction with the carbon double bond of the single-terminated silicone oil to obtain silicone oil modified acrylic polyol.

[0026] Step R2: Mix water and emulsifier to obtain an emulsion phase, wherein the emulsifier is 1.0%-4.0% by mass based on the emulsion phase;

[0027] Step R3: Mix the silicone oil-modified acrylic polyol, fatty acid, and trimethylolpropane (TMP) from Step R1, purge with nitrogen, preheat to 50-70°C, then add isophorone diisocyanate (IPDI), maintain the reaction temperature at 80-90°C until the isophorone diisocyanate (IPDI) has reacted completely, then add the above emulsion phase and mix to obtain the single-end silicone oil-modified acrylic polyurethane copolymer emulsion.

[0028] Furthermore, in step R1, the single-ended silicone oil is a low molecular weight, low viscosity single-ended silicone oil, and the weight-average molecular weight M of the single-ended silicone oil is... w It has a viscosity of 30-100 cp and a solid content of ≥97%.

[0029] Furthermore, in step R1, the single-ended silicone oil can be selected from single-ended acrylate silicone oil.

[0030] Furthermore, in step R1, the bulk polymerization reaction is an atom transfer radical polymerization reaction.

[0031] Further, in step R1, the molar ratio of the acrylic polyol monomer to the single-ended silicone oil is approximately 11 to 20:1.

[0032] Further, in step R1, the weight-average molecular weight M of the silicone oil-modified acrylic polyol is... w The molecular weight distribution is 50,000-80,000, M. w / M n It is 3.2.

[0033] Further, in step R1, the acrylic polyol monomer may be selected from polyethylene glycol diacrylate, such as polyethylene glycol 400 diacrylate water-soluble monomer (PEG(400)DA), or polyethylene glycol methacrylate.

[0034] Further, in step R1, acrylic polyol monomer (AP) is mixed with single-ended silicone oil (M), nitrogen gas is introduced for protection, and the mixture is preheated to 60°C. The temperature is then increased to 90°C within 0.5 hours.

[0035] Further, in step R2, the emulsifier is sodium dodecylbenzenesulfonate and / or fatty alcohol polyoxyethylene ether.

[0036] Furthermore, in step R2, the value of -NCO is continuously determined using the di-n-butylamine method throughout the reaction process until isophorone diisocyanate (IPDI) has completely reacted.

[0037] Further, in step R3, the mass ratio of the silicone oil modified acrylic polyol and fatty acid, trimethylolpropane (TMP), and isophorone diisocyanate (IPDI) is (80-100):(3-6):(5-10):(8-10).

[0038] Further, in step R3, the fatty acid is one or any combination of soybean oleic acid, linolenic acid, ricinoleic acid, or dehydrated ricinoleic acid.

[0039] Furthermore, in step R3, the value of -NCO is continuously determined using the di-n-butylamine method throughout the reaction process until the isophorone diisocyanate (IPDI) has completely reacted.

[0040] Furthermore, the cross-linked nano-inorganic dispersion is at least one of vinyltrimethoxysilane-modified nano-silica aqueous solution, dimethyldialkoxysilane-modified nano-silica aqueous solution, and methylphenyldialkoxysilane-modified nano-silica aqueous solution.

[0041] Furthermore, the dimethyldialkoxysilane-modified nano-silica aqueous solution has a solid content of 25-35% and a particle size of 12-30 nm.

[0042] Furthermore, the preparation method of the dimethyldialkoxysilane-modified nano-silica aqueous solution includes the following steps:

[0043] Step T1: Mix the aqueous solution of hydrophilic silica particles and dimethyldialkoxysilane to obtain a mixed solution;

[0044] Step T2: Adjust the pH of the mixed solution to 4-6, and allow the pH-adjusted mixed solution to undergo a dehydration condensation reaction under the action of a catalyst;

[0045] Step T3: Adjust the pH of the solution after the dehydration condensation reaction to 7.5-9.8 to obtain the dimethyldialkoxysilane-modified nano-silica aqueous solution.

[0046] Further, in step T1, the mass ratio of the aqueous solution of the surface hydrophilic silica particles to the dimethyldialkoxysilane is (90-110):(10-20).

[0047] Furthermore, the preparation methods for the vinyltrimethoxysilane-modified nano-silica aqueous solution and the methylphenyldialkoxysilane-modified nano-silica aqueous solution are respectively carried out with reference to the preparation method for the dimethyldialkoxysilane-modified nano-silica aqueous solution described above.

[0048] Furthermore, in step T2, the catalyst is acrylonitrile and / or cobalt isooctanoate.

[0049] Furthermore, the glaze gloss adjusting powder is at least one of silver-plated flake silica powder, zinc-plated flake silica powder, and aluminum-plated flake silica powder. Preferably, it is silver-plated flake silica powder.

[0050] Further, the pigment and filler are at least one selected from titanium dioxide, talc, calcium sulfate, heavy calcium carbonate, barium sulfate, kaolin, zinc oxide, ceramic micro powder, glass powder, ultrafine alumina, and mica powder. Preferably, the pigment and filler are a mixture composed of titanium dioxide, kaolin, heavy calcium carbonate, ceramic micro powder, glass powder, and ultrafine alumina in a mass ratio of 12-18:0-5:30-50:10-15:10-15:5-10.

[0051] Furthermore, the cellulose is hydroxyethyl cellulose.

[0052] Further, the hydrophobic agent is a fluorinated and / or silicon-containing polymer with an average surface tension of 19.5 × 10⁻⁵ - 21.5 × 10 N / cm after curing. Preferably, the hydrophobic agent is at least one of polyether-modified hydroxyl-containing polydimethylsiloxane, organosilane, and fluorocarbon resin.

[0053] Further, the organosilicon additive is an ultra-high molecular weight organosilicon additive. The molecular weight of the organosilicon additive is 1.2 million to 2 million. Preferably, the ultra-high molecular weight organosilicon additive is at least one of ultra-high molecular weight polydimethyl silicone oil aqueous dispersion and ultra-high molecular weight polyether siloxane aqueous dispersion, and more preferably ultra-high molecular weight polydimethyl silicone oil aqueous dispersion.

[0054] Further, based on the total weight of the water-based interior wall coating, the other additives include 0.05-0.20 wt% wetting agent, 0.4-0.6 wt% dispersant, 0.4-0.8 wt% defoamer, 0.1-0.3 wt% pH adjuster, 0.5-0.7 wt% bactericide and mildew inhibitor, 1.5-3.5 wt% film-forming aid, and 0.4-0.6 wt% antifreeze agent.

[0055] Furthermore, the wetting agent is an APEO-free and readily biodegradable alcohol surfactant.

[0056] Furthermore, the dispersant is a sodium polycarboxylate salt water-based coating dispersant.

[0057] Furthermore, the defoamer is an organosilicone defoamer.

[0058] Furthermore, the pH adjuster is a multifunctional amine auxiliary agent.

[0059] Furthermore, the bactericide and antifungal agent is dibromocyanopropamide or isothiazolinone bactericide.

[0060] Furthermore, the film-forming aid is an alcohol ester solvent.

[0061] Furthermore, the antifreeze agent is propylene glycol.

[0062] This invention also provides a method for preparing the aforementioned environmentally friendly water-based interior wall coating with ceramic glaze effect, the method comprising the following steps:

[0063] Step S1: Mix a portion of the water, a portion of the defoamer, the wetting agent and the dispersant, and stir at a stirring rate of 400-500 r / min for 5-10 min to obtain an additive premix;

[0064] Step S2: Mix the premixed additive liquid, pigments and fillers, glaze gloss adjusting powder and cross-linked nano-inorganic dispersion and stir at a stirring rate of 800-1000 r / min for 5-10 min to obtain a pigment and filler mixture;

[0065] Then, the pigment and filler mixture, cellulose, and pH adjuster are mixed and stirred at a stirring rate of 1200-1500 r / min to obtain a mixed slurry, wherein the fineness of the pigment and filler in the mixed slurry is ≤40 μm;

[0066] Step S3: Mix the mixed slurry and the silicone oil modified acrylic polyurethane copolymer emulsion and stir at a stirring speed of 600-800 r / min to obtain a uniform mixture;

[0067] Then, the homogeneous mixture is mixed evenly with the bactericide, mildew inhibitor, hydrophobic agent, organosilicon additive, film-forming aid, antifreeze agent, remaining defoamer and remaining water to obtain the environmentally friendly water-based interior wall coating with ceramic glaze effect;

[0068] Furthermore, the mass ratio of water in step S1 to water in step S3 is 4-5:1.

[0069] Furthermore, the mass ratio of the defoamer in step S1 to the defoamer in step S3 is 1-1.5:1.

[0070] The beneficial effects of the technical solution of the present invention are as follows:

[0071] 1) In this invention, on the one hand, the silicone oil groups in the side chains of the grafted acrylic polyurethane copolymer emulsion and the vinyl groups in the cross-linked nano-silica can initiate a cross-linking reaction under the action of oxygen, causing the silicone oil-modified acrylic polyurethane copolymer emulsion and the cross-linked silica nanoparticles to cross-link with each other, forming a dense three-dimensional spatial structure of organic polymer-inorganic filler. This can significantly improve the hardness, wear resistance, and durability of the water-based interior wall coating, giving the final water-based interior wall coating excellent scratch resistance. On the other hand, the use of ultra-high molecular weight organosilicon additives further enhances the hardness and wear resistance of the water-based interior wall coating. Simultaneously, the formulation of this invention uses pigments and fillers (glass powder, ceramic micropowder, ultrafine alumina, etc.) with high molar hardness, further improving the scratch resistance and wear resistance of the water-based interior wall coating. The film-forming substance of this invention is a silicone oil-modified acrylic polyurethane emulsion, which has good weather resistance and is easy to clean, exhibiting a ceramic glaze effect.

[0072] 2) In this invention, the addition of flake-shaped coated silica gloss-modifying powder after the water-based interior wall coating has formed a film results in a matte finish at 20° and 60° angles and a high gloss finish at 85° angle, achieving the effect of a ceramic glaze.

[0073] 3) In this invention, the final cross-linked water-based interior wall coating has high density, and the addition of a hydrophobic agent can reduce its surface energy and reduce the adhesion of stains to the coating.

[0074] 4) In this invention, the grafted acrylic polyurethane copolymer emulsion used does not actively add organic solvents, is odorless and environmentally friendly, has a light odor during the coating production and construction process, and the concentration of volatile organic compounds (VOCs) is close to zero, helping people create a green and environmentally friendly living environment that can be occupied immediately.

[0075] 5) The production process of the water-based interior wall coating of this invention is simple and easy to operate, greatly reducing labor and time costs, and is extremely suitable for large-scale production. The construction process of this invention is simple, and it can be applied by roller, brush, and spray, making it extremely suitable for large-area construction. Detailed Implementation

[0076] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

[0077] In the following embodiments and comparative examples:

[0078] The acrylic polyol monomer is a water-soluble monomer of polyethylene glycol 400 diacrylate (PEG(400)DA), which was purchased commercially from Römer Chemical GmbH, Germany.

[0079] The single-ended silicone oil was HY-2900, which was purchased commercially from Huiyan New Materials (Shanghai) Co., Ltd.

[0080] The aqueous solution of hydrophilic silica particles is CH83-130 provided by Guolian Technology, with a silica content of approximately 30±2% and a particle size of 10-20nm; the vinyltrimethoxysilane is XIAMETER OFS-6300 provided by Dow Chemical, with an active ingredient content of approximately 99%.

[0081] The pigments and fillers are composed of titanium dioxide, kaolin, heavy calcium carbonate, ceramic micro powder, glass powder and ultrafine alumina in a mass ratio of 12:5:50:12:12:9. Among them, the titanium dioxide is DuPont 902+, and the other pigments and fillers are not specially formulated.

[0082] The cellulose used is NATROSOL 250HBR supplied by Ashland, and its main component is hydroxyethyl cellulose;

[0083] The hydrophobic agent is TEGO Phobe 1500N provided by Evonik Chemicals, whose main component is hydroxyl-containing polyether-modified polydimethylsiloxane.

[0084] The silicone additive is an ultra-high molecular weight silicone additive, specifically DOWSIL 211S supplied by Dow Chemical.

[0085] Other additives include: wetting agent ECOSURF BD-109 from Dow Chemical; dispersant OROTAN 731A from BASF; defoamer BYK-024 from BYK; pH adjuster AMP-95 from Dow Chemical; bactericides and fungicides ACTICIDE DB 20 and ACTICIDE OTW from Torr; film-forming aid OE300 from Eastman; and antifreeze agent propylene glycol, a general-purpose reagent.

[0086] Example 1

[0087] This embodiment provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. Based on the total mass of the water-based interior wall coating, the water-based interior wall coating comprises the following components by mass percentage:

[0088] Silicone oil modified acrylic polyurethane copolymer emulsion: 16.0 wt%;

[0089] Cross-linked nano-silica dispersion: 12.0 wt%;

[0090] Glaze gloss adjusting powder: 4.0 wt%;

[0091] Pigments and fillers: 35.0 wt%;

[0092] Cellulose: 0.4 wt%;

[0093] Hydrophobic agent: 0.8 wt%;

[0094] Organosilicon additive: 1.0 wt%;

[0095] Other additives: 3.6 wt%; including 0.1 wt% wetting agent, 0.5 wt% dispersant, 0.7 wt% defoamer, 0.2 wt% pH adjuster, 0.6 wt% bactericide and fungicide, 1.0 wt% film-forming aid and 0.5 wt% antifreeze; and

[0096] Deionized water: 27.2 wt%;

[0097] The water-based interior wall coating has a hardness of H, an abrasion resistance of 11.3, a stain resistance of I, and a flame retardancy of A2.

[0098] The preparation method of the above-mentioned environmentally friendly water-based interior wall coating with ceramic glaze effect includes the following steps:

[0099] Step S1: Mix a portion of the water, a portion of the defoamer, the wetting agent and the dispersant, and stir at a stirring rate of 400-500 r / min for 5-10 min to obtain the additive premix;

[0100] Step S2: Mix the premixed additive solution, pigments and fillers, and cross-linked nano-inorganic dispersion at a stirring rate of 800-1000 r / min for 5-10 min to obtain a pigment and filler mixture; mix the pigment and filler mixture, cellulose, and pH adjuster at a stirring rate of 1200-1500 r / min until the fineness of the pigments and fillers in the mixed slurry is ≤40 μm to obtain a mixed slurry;

[0101] Step S3: Mix the mixed slurry and silicone oil-modified acrylic polyurethane and stir evenly at a stirring rate of 600-800 r / min to obtain a homogeneous mixture; mix the homogeneous mixture evenly with bactericide and mildew inhibitor, hydrophobic agent, ultra-high molecular weight organosilicon additive, film-forming aid, antifreeze agent, remaining defoamer and remaining water to obtain an environmentally friendly water-based interior wall coating with ceramic glaze effect.

[0102] The mass ratio of water in step S1 to deionized water in step S3 is 4:1.

[0103] The mass ratio of the defoamer in step S1 to the defoamer in step S3 is 1:1.

[0104] The preparation method of silicone oil modified acrylic polyurethane includes the following steps:

[0105] Step R1: Acrylic polyol monomer (AP) is mixed with single-terminated silicone oil (M), and the mixture is purged with nitrogen for protection. The mixture is preheated to 60°C, and then the temperature is increased further, rising from 60°C to 90°C within 0.5 hours. The reaction is carried out at 80–90°C for 4 hours, allowing the carbon double bonds of the acrylic polyol monomer and the single-terminated silicone oil to undergo bulk polymerization, thus obtaining silicone oil-modified acrylic polyol.

[0106] Step R2: Mix water and emulsifier to obtain an emulsion phase, wherein the emulsifier content is 2.0%;

[0107] Step R3: Mix silicone oil-modified acrylic polyol, fatty acid, and trimethylolpropane (TMP), purge with nitrogen for protection, preheat to 60°C, then add isophorone diisocyanate (IPDI), maintain the reaction temperature at 80-90°C, continuously measure the -NCO value using the di-n-butylamine method during the reaction until the isophorone diisocyanate (IPDI) has reacted completely, then add the above emulsion phase and mix to obtain a single-end silicone oil-modified acrylic polyurethane copolymer emulsion;

[0108] In step R1, the single-ended silicone oil is a low molecular weight, low viscosity single-ended silicone oil, and the weight-average molecular weight M of the single-ended silicone oil is... w It has a value of 1300, a viscosity of 60 cp, and a solid content of 98.0%.

[0109] In step R1, the molar ratio of acrylic polyol monomer to single-ended silicone oil is approximately 16:1.

[0110] In step R1, the weight-average molecular weight M of the silicone oil-modified acrylic polyol is... w The value is 57000, and the molecular weight distribution M is... w / M n It is 3.2.

[0111] In step R2, the emulsifier is sodium dodecylbenzenesulfonate.

[0112] In step R3, the mass ratio of silicone oil-modified acrylic polyol, fatty acid, trimethylolpropane (TMP), and isophorone diisocyanate (IPDI) is 82:4:6:8.

[0113] In step R3, the fatty acid is linoleic acid.

[0114] Example 2

[0115] This embodiment provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. Based on the total mass of the water-based interior wall coating, the water-based interior wall coating comprises the following components by mass percentage:

[0116] Silicone oil modified acrylic polyurethane copolymer emulsion: 12.0 wt%;

[0117] Cross-linked nano-silica dispersion: 15.0 wt%;

[0118] Glaze gloss adjusting powder: 4.0 wt%;

[0119] Pigments and fillers: 35.0 wt%;

[0120] Cellulose: 0.4 wt%;

[0121] Hydrophobic agent: 0.8 wt%;

[0122] Organosilicon additive: 1.0 wt%;

[0123] Other additives: 3.6 wt%; including 0.1 wt% wetting agent, 0.5 wt% dispersant, 0.7 wt% defoamer, 0.2 wt% pH adjuster, 0.6 wt% bactericide and fungicide, 1.0 wt% film-forming aid and 0.5 wt% antifreeze; and

[0124] Deionized water: 28.2 wt%;

[0125] The water-based interior wall coating has a hardness of H, an abrasion resistance of 8.74, a stain resistance of I, and a flame retardancy of A2.

[0126] The preparation method of the above-mentioned environmentally friendly water-based interior wall coating with ceramic glaze effect includes the following steps:

[0127] Step S1: Mix a portion of the water, a portion of the defoamer, the wetting agent and the dispersant, and stir at a stirring rate of 400-500 r / min for 5-10 min to obtain the additive premix;

[0128] Step S2: Mix the premixed additive solution, pigments and fillers, and cross-linked nano-inorganic dispersion at a stirring rate of 800-1000 r / min for 5-10 min to obtain a pigment and filler mixture; mix the pigment and filler mixture, cellulose, and pH adjuster at a stirring rate of 1200-1500 r / min until the fineness of the pigments and fillers in the mixed slurry is ≤40 μm to obtain a mixed slurry;

[0129] Step S3: Mix the mixed slurry and silicone oil-modified acrylic polyurethane and stir evenly at a stirring rate of 600-800 r / min to obtain a homogeneous mixture; mix the homogeneous mixture evenly with bactericide and mildew inhibitor, hydrophobic agent, ultra-high molecular weight organosilicon additive, film-forming aid, antifreeze agent, remaining defoamer and remaining water to obtain an environmentally friendly water-based interior wall coating with ceramic glaze effect.

[0130] The mass ratio of water in step S1 to deionized water in step S3 is 4:1.

[0131] The mass ratio of the defoamer in step S1 to the defoamer in step S3 is 1:1.

[0132] The preparation method of silicone oil modified acrylic polyurethane includes the following steps:

[0133] Step R1: Mix acrylic polyol monomer (AP) with single-terminated silicone oil (M), purge with nitrogen for protection, preheat to 60°C, and continue to raise the temperature from 60°C to 90°C within 0.5 hours. The reaction is carried out at 80-90°C for 4 hours, so that the carbon double bonds of the acrylic polyol monomer and the carbon double bonds of the single-terminated silicone oil undergo a bulk polymerization reaction to obtain silicone oil modified acrylic polyol.

[0134] Step R2: Mix water and emulsifier to obtain an emulsion phase, wherein the emulsifier content is 2.5%;

[0135] Step R3: Mix silicone oil-modified acrylic polyol, fatty acid, and trimethylolpropane (TMP), purge with nitrogen for protection, preheat to 60°C, then add isophorone diisocyanate (IPDI), maintain the reaction temperature at 80-90°C, continuously measure the -NCO value using the di-n-butylamine method during the reaction until the isophorone diisocyanate (IPDI) has reacted completely, then add the above emulsion phase and mix to obtain a single-end silicone oil-modified acrylic polyurethane copolymer emulsion.

[0136] In step R1, the single-ended silicone oil is a low molecular weight, low viscosity single-ended silicone oil, and the weight-average molecular weight M of the single-ended silicone oil is... w It has a value of 1090, a viscosity of 58 cp, and a solid content of 99.0%.

[0137] In step R1, the molar ratio of acrylic polyol monomer to single-ended silicone oil is approximately 17:1.

[0138] In step R1, the weight-average molecular weight M of the silicone oil-modified acrylic polyol is... w The value is 68,000, and the molecular weight distribution is M. w / M n It is 3.2.

[0139] In step R2, the emulsifier is sodium dodecylbenzenesulfonate.

[0140] In step R3, the mass ratio of silicone oil-modified acrylic polyol, fatty acid, trimethylolpropane (TMP), and isophorone diisocyanate (IPDI) is 88:3:6:8.

[0141] In step R3, the fatty acid is soybean oleic acid.

[0142] Example 3

[0143] This embodiment provides an environmentally friendly water-based interior wall coating with a ceramic glaze effect. Based on the total mass of the water-based interior wall coating, the water-based interior wall coating comprises the following components by mass percentage:

[0144] Silicone oil modified acrylic polyurethane copolymer emulsion: 20.0 wt%;

[0145] Cross-linked nano-silica dispersion: 10.0 wt%;

[0146] Glaze gloss adjusting powder: 4.0 wt%;

[0147] Pigments and fillers: 35.0 wt%;

[0148] Cellulose: 0.4 wt%;

[0149] Hydrophobic agent: 0.8 wt%;

[0150] Organosilicon additives: 0.8 wt%;

[0151] Other additives: 3.6 wt%; including 0.1 wt% wetting agent, 0.5 wt% dispersant, 0.7 wt% defoamer, 0.2 wt% pH adjuster, 0.6 wt% bactericide and fungicide, 1.0 wt% film-forming aid and 0.5 wt% antifreeze; and

[0152] Deionized water: 25.2 wt%;

[0153] The water-based interior wall coating has a hardness of H, an abrasion resistance of 10.5, a stain resistance of I, and a flame retardancy of A2.

[0154] The preparation method of the above-mentioned environmentally friendly water-based interior wall coating with ceramic glaze effect includes the following steps:

[0155] Step S1: Mix a portion of the water, a portion of the defoamer, the wetting agent and the dispersant, and stir at a stirring rate of 400-500 r / min for 5-10 min to obtain the additive premix;

[0156] Step S2: Mix the premixed additive solution, pigments and fillers, and cross-linked nano-inorganic dispersion at a stirring rate of 800-1000 r / min for 5-10 min to obtain a pigment and filler mixture; mix the pigment and filler mixture, cellulose, and pH adjuster at a stirring rate of 1200-1500 r / min until the fineness of the pigments and fillers in the mixed slurry is ≤40 μm to obtain a mixed slurry;

[0157] Step S3: Mix the mixed slurry and silicone oil-modified acrylic polyurethane and stir evenly at a stirring rate of 600-800 r / min to obtain a homogeneous mixture; mix the homogeneous mixture evenly with bactericide and mildew inhibitor, hydrophobic agent, ultra-high molecular weight organosilicon additive, film-forming aid, antifreeze agent, remaining defoamer and remaining water to obtain an environmentally friendly water-based interior wall coating with ceramic glaze effect.

[0158] The mass ratio of water in step S1 to deionized water in step S3 is 4:1.

[0159] The mass ratio of the defoamer in step S1 to the defoamer in step S3 is 1:1.

[0160] The preparation method of silicone oil modified acrylic polyurethane includes the following steps:

[0161] Step R1: Mix acrylic polyol monomer (AP) with single-terminated silicone oil (M), purge with nitrogen, preheat to 60°C, and continue to raise the temperature from 60°C to 90°C within 0.5 hours. The reaction is carried out at 80-90°C for 4 hours, so that the carbon double bonds of the acrylic polyol monomer and the carbon double bonds of the single-terminated silicone oil undergo a bulk polymerization reaction to obtain silicone oil modified acrylic polyol.

[0162] Step R2: Mix water and emulsifier to obtain an emulsion phase, wherein the emulsifier content is 1.8%;

[0163] Step R3: Mix silicone oil-modified acrylic polyol, fatty acid, and trimethylolpropane (TMP), purge with nitrogen for protection, preheat to 60°C, then add isophorone diisocyanate (IPDI), maintain the reaction temperature at 80-90°C, continuously measure the -NCO value using the di-n-butylamine method during the reaction until the isophorone diisocyanate (IPDI) has reacted completely, then add the above emulsion phase and mix to obtain a single-end silicone oil-modified acrylic polyurethane copolymer emulsion.

[0164] In step R1, the single-ended silicone oil is a low molecular weight, low viscosity single-ended silicone oil, and the weight-average molecular weight M of the single-ended silicone oil is... w It has a value of 1280, a viscosity of 75 cp, and a solid content of 99.0%.

[0165] In step R1, the molar ratio of acrylic polyol monomer to single-ended silicone oil is approximately 15:1.

[0166] In step R1, the weight-average molecular weight M of the silicone oil-modified acrylic polyol is... w The value is 71000, and the molecular weight distribution M w / M n It is 3.2.

[0167] In step R2, the emulsifier is sodium dodecylbenzenesulfonate.

[0168] In step R3, the mass ratio of silicone oil-modified acrylic polyol, fatty acid, trimethylolpropane (TMP), and isophorone diisocyanate (IPDI) is 92:5:7:9.

[0169] In step R3, the fatty acid is ricinoleic acid.

[0170] Comparative Example 1

[0171] This comparative example provides a water-based interior wall coating with a ceramic glaze effect. The only difference between this comparative example and Example 1 is that:

[0172] This comparative example uses an acrylic emulsion with a glass transition temperature (Tg) of 50°C instead of a silicone oil-modified acrylic polyurethane copolymer emulsion.

[0173] The silica dispersion in this comparative example was not surface-treated. The aqueous solution of surface-hydrophilic silica particles was CH83-130 provided by Guolian Technology, with a particle size of 15-20 nm.

[0174] The preparation method of this comparative example is as described in Example 1.

[0175] Comparative Example 2

[0176] This comparative example provides a water-based interior wall coating with a ceramic glaze effect. The only difference between this comparative example and Example 1 is that:

[0177] This comparative example uses a self-crosslinking acrylic emulsion, JONCRYL 1980, purchased from BASF, instead of the silicone oil-modified acrylic polyurethane copolymer emulsion of Example 1.

[0178] This comparative example does not use an aqueous solution of nano-silica modified with vinyltrimethoxysilane (crosslinked nano-silica dispersion).

[0179] The preparation method of this comparative example is as described in Example 1.

[0180] Comparative Example 3

[0181] This comparative example provides a water-based interior wall coating with a ceramic glaze effect. The only difference between this comparative example and Example 1 is that:

[0182] This comparative example uses a two-component system of high-hydroxyl-value hydroxyl acrylic resin (hydroxyl value of about 5%) and water-dispersible isocyanate instead of the silicone oil-modified acrylic polyurethane copolymer emulsion of Example 1.

[0183] This comparative example does not use an aqueous solution of nano-silica modified with vinyltrimethoxysilane (crosslinked nano-silica dispersion).

[0184] The preparation method of this comparative example is as described in Example 1.

[0185] Table 1. Amounts (wt%) of each component in Comparative Examples 1-3

[0186]

[0187]

[0188] Test case

[0189] The water-based interior wall coatings prepared in Examples 1-3 and Comparative Examples 1-3 were tested for their basic properties and stain resistance according to GB / T9756-2018 "Synthetic Resin Emulsion Interior Wall Coatings" and HG / T4756-2014 "Interior Wall Stain-Resistant Latex Coatings"; their abrasion resistance was tested according to GB / T1768-2006 "Determination of Abrasion Resistance of Paints and Varnishes - Rotating Rubber Grinding Wheel Method"; and their flammability was tested according to GB 8624-2012 "Classification of Burning Performance of Building Materials and Products". Simultaneously, red, black, and blue water-based markers and Hero brand blue-black ink were used to write on the coating surface. After 30 minutes, the surface was wiped with a damp towel. For oil-based markers, after 30 minutes, the surface was wiped with 95% alcohol test paper. The ease of cleaning of the coating was assessed based on the ease of wiping and the marks left after wiping.

[0190] The results of the main performance tests are shown in Tables 2 and 3.

[0191] Table 2 Standard test results of Examples 1-3

[0192]

[0193]

[0194] Table 3 Standard test results for comparative examples 1-3

[0195]

[0196] As can be seen from the experimental results in Tables 2 and 3, the water-based interior wall coatings with ceramic glaze effect prepared in Examples 1-3 have excellent scratch resistance, abrasion resistance, stain resistance, a certain degree of anti-graffiti properties, and excellent solvent resistance. The properties of Comparative Examples 1-3 are significantly inferior to those of the Examples: Comparative Example 1 uses a high-Tg acrylic emulsion as the film-forming substance, which can only guarantee a certain film hardness and lacks sufficient stain resistance and hydrophobicity. Although a certain amount of hydrophobic agent is added, its effect in the coating formulation is limited. Except for the washability, all other properties are unqualified. Comparative Example 2 uses self-crosslinking acrylic resin as the film-forming substance, which guarantees both a certain film hardness and the density of the film after formation, and has a certain degree of stain resistance. However, its stain resistance is limited by the relatively few hydrophobic groups on the main chain of the film-forming substance, resulting in only average stain resistance. While its solvent resistance and water-based pen erasability are satisfactory, other properties are unsatisfactory. Comparative Example 3 uses a two-component polyurethane as the film-forming material, resulting in a high film hardness that ensures scratch resistance and stain resistance. It can easily remove water-based stains, but its ability to remove ink stains is somewhat insufficient. The organic content of all comparative examples is relatively high, hence their low fire resistance rating.

[0197] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any modifications or equivalent changes made based on the technical essence of the present invention shall still fall within the scope of protection claimed by the present invention.

Claims

1. An environmentally friendly water-based interior wall coating with a ceramic glaze effect, characterized in that, Based on the total mass of the interior wall coating, the water-based interior wall coating consists of the following components by mass percentage: Silicone oil modified acrylic polyurethane copolymer emulsion: 10.0-20.0 wt%; Cross-linked nano-inorganic dispersions: 10.0-16.0 wt%; Glaze gloss adjusting powder: 1.0-5.0%; Pigments and fillers: 30.0-40.0 wt%; Cellulose: 0.3-0.5 wt%; Hydrophobic agent: 0.5-2.0 wt%; Organosilicon additives: 0.5%-1.5%; Other additives: 2.5-4.5 wt%; The other additives are at least one selected from wetting agents, dispersants, defoamers, pH adjusters, bactericides and fungicides, film-forming aids, and antifreeze agents; and Water: 15.0-35.0wt%; The silicone oil-modified acrylic polyurethane copolymer emulsion has a polymer side chain with a grafting rate of 7-8% silicone oil groups, the silicone oil-modified acrylic polyurethane copolymer emulsion has a weight-average molecular weight of 90,000-140,000, and a molecular weight distribution Mw / Mn of 2-4. The cross-linked nano-inorganic dispersion is at least one of vinyltrimethoxysilane-modified nano-silica aqueous solution, dimethyldialkoxysilane-modified nano-silica aqueous solution, and methylphenyldialkoxysilane-modified nano-silica aqueous solution. The preparation method of the silicone oil modified acrylic polyurethane copolymer emulsion includes: Step R1: Mix acrylic polyol monomer with single-ended silicone oil, purge with nitrogen, preheat to 50-70℃, and continue to raise the temperature to 85-105℃ within 0.3-1h, so that the reaction can proceed at this temperature and continue for 4-6 hours. The carbon double bond of the acrylic polyol monomer undergoes a bulk polymerization reaction with the carbon double bond of the single-ended silicone oil to obtain silicone oil modified acrylic polyol. Step R2: Mix water and an emulsifier to obtain an emulsion phase, wherein the emulsifier is 1.0%-4.0% by mass based on the emulsion phase; Step R3: Mix the silicone oil-modified acrylic polyol, fatty acid, and trimethylolpropane from Step R1, purge with nitrogen, preheat to 50-70°C, then add isophorone diisocyanate, maintain the reaction temperature at 80-90°C until the isophorone diisocyanate has reacted completely, then add the above emulsion phase and mix to obtain the single-end silicone oil-modified acrylic polyurethane copolymer emulsion.

2. The water-based interior wall coating according to claim 1, characterized in that, In step R1, the single-ended silicone oil has a weight-average molecular weight (Mw) of 400-2000, a viscosity of 30-100 cp, and a solid content of ≥97%.

3. The water-based interior wall coating according to claim 2, characterized in that, In step R1, the weight-average molecular weight Mw of the silicone oil-modified acrylic polyol is 50,000-80,000, and the molecular weight distribution Mw / Mn is 3.

2.

4. The water-based interior wall coating according to claim 1, characterized in that, The dimethyldialkoxysilane-modified nano-silica aqueous solution has a solid content of 25-35% and a particle size of 12-30 nm.

5. The water-based interior wall coating according to claim 1, characterized in that, Based on the total weight of the water-based interior wall coating, the other additives are 0.05-0.20 wt% wetting agent, 0.4-0.6 wt% dispersant, 0.4-0.8 wt% defoamer, 0.1-0.3 wt% pH adjuster, 0.5-0.7 wt% bactericide and mildew inhibitor, 1.5-3.5 wt% film-forming aid, and 0.4-0.6 wt% antifreeze agent.

6. A method for preparing an environmentally friendly water-based interior wall coating with a ceramic glaze effect as described in any one of claims 1-5, characterized in that, The preparation method includes the following steps: Step S1: Mix a portion of the water, a portion of the defoamer, the wetting agent and the dispersant, and stir at a stirring rate of 400-500 r / min for 5-10 min to obtain an additive premix; Step S2: Mix the premixed additive solution, pigments and fillers, glaze gloss adjusting powder and cross-linked nano-inorganic dispersion and stir at a stirring rate of 800-1000 r / min for 5-10 min to obtain a pigment and filler mixture; then mix the pigment and filler mixture, cellulose and pH adjuster and stir at a stirring rate of 1200-1500 r / min to obtain a mixed slurry, wherein the fineness of the pigments and fillers in the mixed slurry is ≤40 μm; Step S3: Mix the mixed slurry and the silicone oil modified acrylic polyurethane copolymer emulsion and stir at a stirring speed of 600-800 r / min to obtain a uniform mixture; Then, the homogeneous mixture is mixed evenly with the bactericide, mildew inhibitor, hydrophobic agent, organosilicon additive, film-forming aid, antifreeze agent, remaining defoamer and remaining water to obtain the environmentally friendly water-based interior wall coating with ceramic glaze effect.

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