Reflective heat-insulating rock slice real stone paint and preparation method and application thereof

Abstract

The application relates to the field of building outer wall decoration materials, in particular to a reflective heat-insulating rock piece real stone paint and a preparation method and application thereof. The reflective heat-insulating rock piece real stone paint is prepared from the following raw materials in percentage by mass: reflective heat-insulating color paste 1-8%, reflective heat-insulating composite rock piece 5-15%, base paint 20-35%, and the rest is supplemented with color sand. The rock piece real stone paint prepared finally not only meets the appearance and reflective heat-insulating requirements of existing consumers for building outer wall decoration materials, but also has excellent hydrophobicity, weather resistance, stain resistance and self-cleaning performance; especially, the rock piece real stone paint can maintain excellent reflective performance in a high-brightness environment, reduce the water absorption of the coating, improve the hydrophobic self-cleaning property, effectively avoid the problems of cracking, peeling and decreased reflective capacity of the existing real stone paint in use, and has very excellent application prospect.

Description

Technical Field

[0001] This application relates to the field of building exterior wall decoration materials, and in particular to a reflective and heat-insulating rock chip real stone paint, its preparation method and application. Background Technology

[0002] In recent years, with the acceleration of urbanization and the improvement of people's living standards, the demand for building exterior wall decoration materials has been increasing. Traditional exterior wall decoration materials such as tiles and marble, while beautiful and durable, suffer from problems such as complex construction, high cost, and easy detachment, and lack energy-saving properties. In contrast, real stone paint, as a new type of environmentally friendly exterior wall decoration material, is favored by the market due to its low resource consumption, ease of construction and renewal, lack of safety hazards, and rich variety of colors and types. Especially against the backdrop of energy conservation and emission reduction becoming a social consensus, the development of real stone paint with reflective heat insulation functions is particularly important.

[0003] Currently, there are some reflective heat-insulating stone-like paint products on the market. These products enhance the coating's ability to reflect solar radiation heat by adding specific reflective heat-insulating materials. However, existing reflective heat-insulating stone-like paints still face some problems, such as: uneven distribution of reflective heat-insulating materials in some products, resulting in low overall reflectivity and insufficient ability to reduce building surface temperature; insufficient adhesion strength of some reflective heat-insulating stone-like paints on different substrates, which may lead to peeling, especially under extreme climatic conditions; and poor water repellency, weather resistance, and stain resistance, resulting in a significant decrease in reflectivity when the coating is contaminated.

[0004] Therefore, in order to effectively solve the above problems, this application provides a reflective and heat-insulating rock-flake stone paint and its preparation method. The rock-flake stone paint finally obtained by this application not only meets the current consumer demand for aesthetics and reflective heat insulation in building exterior wall decoration materials, but also maintains excellent water-repellent, weather-resistant, stain-resistant, and self-cleaning properties; in particular, it can maintain excellent reflective performance in high-brightness environments, reduce coating water absorption, and improve hydrophobic self-cleaning properties, effectively avoiding the problems of cracking, peeling, and decreased reflectivity that occur in existing stone paints during use, and has very promising application prospects. Summary of the Invention

[0005] To address the aforementioned issues, the first aspect of this application provides a reflective and heat-insulating rock-flake real stone paint, wherein the raw materials, by mass percentage, are: 1-8% reflective and heat-insulating color paste, 5-15% reflective and heat-insulating composite rock flakes, 20-35% base paint, and colored sand as a supplement.

[0006] As a preferred embodiment, the mass ratio of the reflective heat-insulating color paste, the reflective heat-insulating composite rock sheet, and the base paint is (2~5):(5~10):(25~30).

[0007] As a preferred embodiment, the mass ratio of the reflective heat-insulating color paste, the reflective heat-insulating composite rock sheet, and the base paint is (3~4):(7~9):(26~28).

[0008] As a preferred embodiment, the reflective heat-insulating pigment paste, by mass percentage, comprises: 20-30% reflective heat-insulating pigment, 3-5% dispersant I, 1.5-2.5% wetting agent I, 1-3% cellulose ether I, 0.5-0.8% defoamer, 2-2.5% film-forming aid I, 0.3-0.5% rheology modifier I, with deionized water to make up the balance.

[0009] As a preferred embodiment, the dispersant I is polyvinylpyrrolidone or a polycarboxylate.

[0010] As a preferred embodiment, the dispersant I is polyvinylpyrrolidone.

[0011] As a preferred embodiment, the wetting agent I is ethylene bis-stearamide or polyoxyethylene glycerol tristearate.

[0012] As a preferred embodiment, the wetting agent I is ethylene bis-stearamide.

[0013] As a preferred embodiment, the cellulose ether I is at least one of hydroxyethyl cellulose ether, hydroxypropyl cellulose ether, and hydroxyethyl methyl cellulose ether.

[0014] As a preferred embodiment, the cellulose ether I is hydroxyethyl cellulose ether.

[0015] As a preferred embodiment, the film-forming aid I is at least one of dodecyl alcohol ester, hexadecyl alcohol ester, and sorbitan tristearate.

[0016] As a preferred embodiment, the film-forming aid I is a dodecyl alcohol ester.

[0017] As a preferred embodiment, the rheology modifier I is organically modified bentonite or sodium polyacrylate.

[0018] As a preferred embodiment, the rheology modifier I is sodium polyacrylate.

[0019] As a preferred embodiment, the reflective heat-insulating composite rock sheet comprises, by mass percentage, the following raw materials: 6-10% reflective heat-insulating pigment, 10-12% aluminum silicate, 20-30% composite solid material, 30-35% water-based acrylic emulsion, 8-10% water-based polyurethane emulsion, 0.2-0.5% cellulose ether ⅠⅠ, 0.3-0.6% dispersant ⅠⅠ, 0.1-0.2% wetting agent ⅠⅠ, 0.2-0.3% pH adjuster, 0.3-0.7% defoamer, 0.3-0.5% bactericide and mildew inhibitor, 0.5-1% polysiloxane, 1-2% film-forming aid ⅠⅠ, 0.1-0.3% rheology modifier ⅠⅠ, with deionized water to make up the balance.

[0020] As a preferred embodiment, the composite solid material is a composition of talc, heavy calcium carbonate, and modified titanium-based particles.

[0021] As a preferred embodiment, the mass ratio of the talc powder, heavy calcium carbonate and modified titanium-based particles is (6~10):(10~15):(8~14).

[0022] As a preferred embodiment, the mass ratio of the talc powder, heavy calcium carbonate and modified titanium-based particles is (8~9):(11~13):(9~11).

[0023] As a preferred embodiment, the talc powder has an average particle size of 1.5~2μm.

[0024] As a preferred embodiment, the average particle size of the heavy calcium carbonate is 0.5~1.5μm.

[0025] As a preferred embodiment, the preparation method of the modified titanium-based particles specifically includes the following steps: S1: Titanium dioxide, zinc oxide, succinic anhydride, and γ-aminopropylmethyldiethoxysilane are mixed and added to N,N-dimethylformamide solvent to obtain pretreated particles; S2: The pretreated particles, tetrabutyl titanate, and 1,4-naphthalenedicarboxylic acid are mixed and added to N,N-dimethylacetamide solvent, and 2-methylimidazole, p-aminobenzoic acid, and hydrofluoric acid are added to continue the reaction; S3: After the reaction is completed, the mixture is cooled to room temperature, centrifuged and filtered to obtain a solid product, washed with N,N-dimethylformamide and deionized water, and then vacuum dried to obtain the final product;

[0026] As a preferred embodiment, the preparation method of the modified titanium-based particles specifically includes the following steps: S1: Titanium dioxide, zinc oxide, succinic anhydride, and γ-aminopropylmethyldiethoxysilane are mixed and added to N,N-dimethylformamide solvent, ultrasonically dispersed at 400~500W for 30~35min, then heated to 65~70℃, ultrasonically maintained at this temperature for 2~2.5h, then centrifuged and filtered, washed with ethanol and dried to obtain pretreated particles; S2: The pretreated particles, tetrabutyl titanate, and 1,4-naphthalenedicarboxylic acid are mixed and added to... In N,N-dimethylacetamide solvent, heat to 50-60℃ and ultrasonically disperse at 400-500W for 30-35 min. Then heat to 90-95℃ and keep reacting for 5-6 h. Add 2-methylimidazole, p-aminobenzoic acid and hydrofluoric acid, heat to 110-120℃ and keep reacting for 13-16 h. S3: After the reaction is complete, cool to room temperature, centrifuge and filter to obtain solid product. Wash with N,N-dimethylformamide and deionized water 2-3 times, then vacuum dry at 80-85℃ for 8-10 h to obtain the final product.

[0027] As a preferred embodiment, the titanium dioxide has an average particle size of 10-15 nm.

[0028] As a preferred embodiment, the mass ratio of titanium dioxide, zinc oxide, succinic anhydride and γ-aminopropylmethyldiethoxysilane is (1~1.2):(0.1~0.2):(0.3~0.4):(0.05~0.1).

[0029] As a preferred embodiment, the mass ratio of the pretreated particles, tetrabutyl titanate, 1,4-naphthalenedicarboxylic acid, 2-methylimidazole and p-aminobenzoic acid is (1.2~1.5):(2.5~3):(2.2~2.6):(0.3~0.5):(0.4~0.6).

[0030] In this application, by adding modified titanium-based particles to the reflective heat-insulating composite rock sheet, the reflective heat insulation, water repellency, and stain resistance and self-cleaning properties of the rock sheet real stone paint can be effectively improved. The added modified titanium-based particles can form a multi-microporous structure with micro-nano particles as the outer coating and composite framework particles as the internal main body. The presence of this structure can significantly enhance the maintenance effect of the modified titanium-based particles on surface oxidation molecules, thereby maintaining the oxidation and decomposition of organic pollutants on the surface of the stone paint during long-term use, thus achieving the stain-resistant and self-cleaning effect of the stone paint surface. Moreover, the presence of the multi-microporous structure promotes the formation of more groove surface structures on the stone paint surface, which in turn blocks surface water molecules during long-term use, preventing them from continuously agglomerating and forming a continuous surface water layer phase. This prevents water molecules from penetrating through the hydration layer on the stone paint surface, significantly improving its water resistance. On the other hand, the formed complex framework structure can significantly improve the electronic vibration effect of surface titanium dioxide particles, thereby significantly increasing the overall infrared refractive index of the modified titanium-based particles, inhibiting its subsequent conversion efficiency of photothermal energy, and increasing the light penetration resistance through its light scattering phenomenon, improving the reflection efficiency, and thus obtaining good reflective heat insulation performance.

[0031] As a preferred embodiment, the solid content of the waterborne polyurethane emulsion is 35-42%.

[0032] As a preferred embodiment, the viscosity of the aqueous polyurethane emulsion is 1000~3000 mPa·s, and the temperature condition is 25℃.

[0033] As a preferred embodiment, the cellulose ether ⅠⅠ is at least one of hydroxypropyl methylcellulose ether, hydroxypropyl methylcellulose ether, or carboxymethylcellulose ether.

[0034] As a preferred embodiment, the cellulose ether ⅠⅠ is hydroxypropyl methylcellulose ether.

[0035] As a preferred embodiment, the dispersant ⅠⅠ is an ammonium polycarboxylate or sodium acrylate.

[0036] As a preferred embodiment, the dispersant ⅠⅠ is a polycarboxylate ammonium salt.

[0037] As a preferred embodiment, the wetting agent ⅠⅠ is at least one of PEG-20 oleate, polysorbate 80, and polyoxyethylene glycerol tristearate.

[0038] As a preferred embodiment, the wetting agent ⅠⅠ is polysorbate 80.

[0039] As a preferred embodiment, the film-forming aid ⅠⅠ is at least one of dodecyl alcohol ester, hexadecyl alcohol ester acetate, and propylene glycol phenyl ether.

[0040] As a preferred embodiment, the film-forming aid ⅠⅠ is hexadecyl acetate.

[0041] As a preferred embodiment, the rheology modifier ⅠⅠ is at least one of polyurethane rheology modifiers.

[0042] As a preferred embodiment, the reflective heat-insulating pigment in the reflective heat-insulating color paste and the reflective heat-insulating composite rock sheet raw material is at least one of titanium dioxide W800, iron oxide yellow, cobalt green, cobalt blue, titanium nickel yellow, zinc iron yellow and chrome iron black.

[0043] As a preferred embodiment, the reflective heat-insulating pigment in the reflective heat-insulating color paste and the reflective heat-insulating composite rock sheet raw material is at least one of titanium dioxide W800, iron oxide yellow, titanium nickel yellow, zinc iron yellow and cobalt blue.

[0044] As a preferred embodiment, the base paint, by weight percentage, comprises: 48-50% water-based acrylic emulsion, 0.2-0.3% pH adjuster, 0.2-0.5% bactericide and mildew inhibitor, 1-2% polysiloxane, 0.2-0.5% defoamer, 0.6-1% cellulose ether ⅠⅠⅠ, 2.5-3% film-forming aid ⅠⅠⅠ, 0.1-0.5% rheology modifier ⅠⅠⅠ, 0.2-0.5% antifreeze, 0.5-1.5% modifying agent, and deionized water to make up the balance.

[0045] As a preferred embodiment, the cellulose ether ⅠⅠⅠ is hydroxyethyl methyl cellulose ether.

[0046] As a preferred embodiment, the film-forming aid ⅠⅢ is at least one of hexadecyl acetate, propylene glycol phenyl ether, or dodecyl acetate.

[0047] As a preferred embodiment, the film-forming aid ⅠⅠⅠ is propylene glycol phenyl ether.

[0048] As a preferred embodiment, the rheology modifier ⅠⅢⅠ is sodium polyacrylate.

[0049] As a preferred embodiment, the antifreeze is a combination of diethylene glycol and propylene glycol.

[0050] As a preferred embodiment, the mass ratio of diethylene glycol to propylene glycol is (4~5):(1~1.5).

[0051] As a preferred embodiment, the preparation method of the modified additive specifically includes the following steps: S1: Add octamethylcyclotetrasiloxane to deionized water and heat and stir; S2: After stirring, add aminopropyltriethoxysilane, sodium dodecyl sulfate, γ-methacryloyloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate in sequence, stir to react, add benzoyl peroxide, and keep the reaction at a constant temperature; S3: After the reaction is complete, slowly add ammonia water, control the pH of the system to 7.5~8, then cool naturally to room temperature, sieve the product, wash, and obtain the final product;

[0052] As a preferred embodiment, the preparation method of the modified additive specifically includes the following steps: S1: Add deionized water to a high-speed stirrer, stir at room temperature for 5-10 minutes at a speed of 800-1000 rpm to ensure a suitable water temperature, add octamethylcyclotetrasiloxane, heat to 60-65℃, and stir at a speed of 400-800 rpm for 30-40 minutes; S2: After stirring is complete, add aminopropyltriethoxysilane and sodium dodecyl sulfate sequentially, adding 400-800 ml each time. Stir at rpm for 15-20 min, then add γ-methacryloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate sequentially and continue stirring for 30-35 min. After stirring, heat to 80-90℃, add benzoyl peroxide, and keep the reaction at this temperature for 3-5 h. S3: After the reaction is complete, slowly add ammonia water to control the pH of the system to 7.5-8, then let it cool naturally to room temperature. Filter the product through a 500-600 mesh sieve and wash with ethanol. The product is then obtained.

[0053] As a preferred embodiment, the mass ratio of the octamethylcyclotetrasiloxane, aminopropyltriethoxysilane and sodium dodecyl sulfate is (25~30):(15~20):(5~6).

[0054] As a preferred embodiment, the mass ratio of octamethylcyclotetrasiloxane, γ-methacryloyloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate is (25~30):(7~10):(5~8):(5~8).

[0055] In this application, the addition of modified additives enables the repulsion of water molecules within the stone paint through the siloxane and acrylate long chains and corresponding groups contained therein, reducing the rate of water penetration and increasing the penetration resistance. On the other hand, it is easier to form a barrier film layer. The presence of this film layer not only achieves the barrier effect against water molecules in the system, but also reduces the humidity of the system. Moreover, the more robust multi-layer cross-linked network formed by it can form micro-chemical bonds with other raw materials of the stone paint, fully increasing the mutual adhesion between molecular chains. Thus, during use, it significantly improves the resistance of the stone paint system to molecular chain slippage, enhances the overall toughness and mechanical properties, and reduces the breakage caused by molecular chain slippage, thereby ensuring the anti-cracking and anti-peeling properties of the stone paint and ensuring the stability of its reflective heat insulation performance.

[0056] As a preferred embodiment, the solid content of the water-based acrylic emulsion in the reflective heat-insulating composite rock sheet and the base paint raw material is 45-52%, the viscosity is 2500-4000 mPa·s, and the temperature condition is 25℃.

[0057] As a preferred embodiment, the defoamer in the reflective heat-insulating color paste, the reflective heat-insulating composite rock sheet, and the base paint raw material is any one of the organosilicon defoamers.

[0058] As a preferred embodiment, the pH adjuster in the reflective heat-insulating composite rock sheet and the base paint raw material is at least one of sodium hydroxide, ammonia, potassium hydroxide and diethanol.

[0059] As a preferred embodiment, the pH adjuster in the reflective heat-insulating composite rock sheet and the base paint raw material is sodium hydroxide.

[0060] As a preferred embodiment, the bactericide and mildew inhibitor in the reflective heat-insulating composite rock sheet and the base paint raw material is isothiazolinone or dioxane.

[0061] As a preferred embodiment, the bactericide and mildew inhibitor in the reflective heat-insulating composite rock sheet and the base paint raw material is isothiazolinone.

[0062] As a preferred embodiment, the polysiloxane in the reflective heat-insulating composite rock sheet and the base paint raw material is at least one of polydimethylsiloxane, hydroxyl-terminated polydimethylsiloxane, polyether-modified polysiloxane, and fluorosiloxane.

[0063] As a preferred embodiment, the polysiloxane in the reflective heat-insulating color paste, reflective heat-insulating composite rock sheet, and base paint raw material is hydroxyl-terminated polydimethylsiloxane.

[0064] As a preferred embodiment, the colored sand is reflective and heat-insulating colored sand.

[0065] The second aspect of this application provides a method for preparing the above-mentioned reflective heat-insulating rock flake real stone paint, specifically including the following steps: S1: The reflective heat-insulating color paste raw materials are stirred in a high-speed mixing kettle at 1000~1500 rpm for 40~60 min until uniformly dispersed, and then ground in a sand mill, and then passed through a 400~500 mesh sieve to remove large particles to obtain reflective heat-insulating color paste; S2: The reflective heat-insulating composite rock flake raw materials are stirred in a high-speed mixing kettle at 1000~1500 rpm for 35~45 min until uniformly dispersed, and then ground in a sand mill. After grinding, an intermediate is obtained. The intermediate is mixed and stirred with reflective heat-insulating pigment to create color. Then, through coating, drying, crushing, and sieving processes, reflective heat-insulating composite rock sheets after coloring with reflective heat-insulating pigment are obtained. S3: The raw materials of the base paint are stirred in a high-speed mixing kettle at 1000~1500rpm for 40~60min until they are evenly dispersed to obtain the base paint. Finally, the reflective heat-insulating composite rock sheets after coloring with reflective heat-insulating pigment, the base paint, and the colored sand are stirred in a high-speed mixing kettle at 600~800rpm until they are evenly dispersed and the paint is uniform without layering.

[0066] The third aspect of this application defines the application of the aforementioned reflective and heat-insulating rock chip paint in commercial building exterior wall coatings, residential building exterior wall coatings, industrial plant exterior wall coatings, and cold storage building exterior wall coatings.

[0067] The beneficial effects of this application are:

[0068] 1. The reflective and heat-insulating rock chip real stone paint provided in this application not only meets the existing consumer demand for aesthetics and reflective heat insulation of building exterior wall decoration materials, but also maintains excellent water repellency, weather resistance, stain resistance and self-cleaning properties; in particular, it can maintain excellent reflective performance in high-brightness environments, reduce the water absorption of the coating, improve hydrophobic self-cleaning properties, and effectively avoid the problems of cracking, peeling and reduced reflectivity that occur in the use of existing real stone paints, and has very good application prospects.

[0069] 2. The reflective and heat-insulating rock-chip real stone paint provided in this application incorporates modified titanium-based particles that form a multi-microporous structure with micro-nano particles as the outer coating and composite skeleton particles as the inner main body. The presence of this structure can significantly enhance the maintenance effect of modified titanium-based particles on surface oxidation molecules, thereby maintaining the oxidation and decomposition of organic pollutants on the surface of the real stone paint during long-term use, thus achieving the stain-resistant and self-cleaning effect of the real stone paint surface. Furthermore, the presence of the multi-microporous structure promotes the formation of more groove surface structures on the real stone paint surface, thereby blocking surface water molecules during long-term use and preventing their continuous aggregation to form a continuous surface water layer phase. This prevents water molecules from penetrating the surface of the real stone paint through the hydration layer, significantly improving its water resistance.

[0070] 3. The rock-chip real stone paint with reflective heat insulation provided in this application has a complex skeleton structure formed by the added modified titanium-based particles, which can greatly improve the electronic vibration effect of the surface titanium dioxide particles, thereby greatly improving the overall infrared refractive index of the modified titanium-based particles, suppressing its subsequent conversion efficiency of photothermal energy, and increasing the light penetration resistance through its light scattering phenomenon, thereby improving the reflection efficiency and obtaining good reflective heat insulation performance.

[0071] 4. The reflective heat-insulating rock-flake real stone paint provided in this application incorporates a modifying agent that, through its contained siloxane and acrylate long chains and corresponding groups, can repel water molecules within the real stone paint, reducing the rate of water penetration and increasing penetration resistance. On the other hand, it more easily forms a barrier film layer. The presence of this film layer can achieve a barrier effect against water molecules in the system, reducing system humidity. Furthermore, the more robust multi-layered cross-linked network it forms can form micro-chemical bonds with other raw materials of the real stone paint, significantly increasing the mutual adhesion between molecular chains. This greatly improves the resistance of the real stone paint system to molecular chain slippage during use, enhances overall toughness and mechanical properties, and reduces breakage caused by molecular chain slippage, thereby ensuring the crack resistance and peeling resistance of the real stone paint and guaranteeing the stability of its reflective heat-insulating performance. Detailed Implementation

[0072] The following will further illustrate and demonstrate the technical solutions described above in this application through specific implementation schemes. Furthermore, the following embodiments are merely practical examples used to illustrate and explain the content of the technical solutions in the specification, and should not limit the scope of the claims to be protected by this application. All technical products based on the technical solutions described in this application should be covered within the scope of protection of this application.

[0073] In the following embodiments, unless otherwise specified, the raw materials are all commercially available products or can be prepared by methods known to those skilled in the art.

[0074] Example 1

[0075] Example 1 provides a reflective and heat-insulating rock chip real stone paint, the raw materials of which are: 3.6% reflective and heat-insulating color paste, 8.8% reflective and heat-insulating composite rock chips, 28.5% base paint, and colored sand as a supplement.

[0076] The reflective heat-insulating color paste, by mass percentage, consists of: 25% reflective heat-insulating pigment, 4.2% dispersant I, 1.8% wetting agent I, 2.1% cellulose ether I, 0.6% defoamer, 2.1% film-forming aid I, 0.4% rheology modifier I, and the balance being deionized water.

[0077] Dispersant I is polyvinylpyrrolidone K30; wetting agent I is ethylene bis-stearamide; cellulose ether I is hydroxyethyl cellulose ether; film-forming aid I is dodecyl alcohol ester; rheology modifier I is sodium polyacrylate, which was purchased from Dow Chemical (Shanghai) Co., Ltd. as TT-935 product.

[0078] The reflective heat-insulating composite rock sheet, by mass percentage, contains the following raw materials: 8.6% reflective heat-insulating pigment, 11.4% aluminum silicate, 28.8% composite solids, 32.5% waterborne acrylic emulsion, 9.1% waterborne polyurethane emulsion, 0.4% cellulose ether ⅠⅠ, 0.5% dispersant ⅠⅠ, 0.16% wetting agent ⅠⅠ, 0.22% pH adjuster, 0.4% defoamer, 0.32% bactericide and mildew inhibitor, 0.75% polysiloxane, 1.6% film-forming aid ⅠⅠ, 0.21% rheology modifier ⅠⅠ, with deionized water to make up the balance.

[0079] The composite solid material is a combination of talc powder, heavy calcium carbonate and modified titanium-based particles, with a mass ratio of 8.3:12.5:10.

[0080] The average particle size of talc is 1.8 μm; the average particle size of heavy calcium carbonate is 1.1 μm.

[0081] The preparation method of modified titanium-based particles specifically includes the following steps, in parts by mass: S1: 1.2 parts of titanium dioxide, 0.18 parts of zinc oxide, 0.35 parts of succinic anhydride, and 0.08 parts of γ-aminopropylmethyldiethoxysilane are mixed and added to 60 parts of N,N-dimethylformamide solvent, ultrasonically dispersed at 420W for 30 min, then heated to 68℃, ultrasonically maintained for 2.2 h, then centrifuged and filtered, washed with ethanol and dried to obtain pretreated particles; S2: 1.4 parts of pretreated particles, 2.6 parts of tetrabutyl titanate, and 2. Four parts of 1,4-naphthalenedicarboxylic acid were mixed and added to 120 parts of N,N-dimethylacetamide solvent. The mixture was heated to 60℃ and ultrasonically dispersed at 450W for 30 min. Then, the mixture was heated to 90℃ and kept at that temperature for 5.5 h. Then, 0.45 parts of 2-methylimidazole, 0.5 parts of p-aminobenzoic acid and 0.8 parts of hydrofluoric acid were added and the mixture was heated to 120℃ and kept at that temperature for 15 h. S3: After the reaction was completed, the mixture was cooled to room temperature, centrifuged and filtered to obtain a solid product. The solid product was washed twice with N,N-dimethylformamide and deionized water. Then, it was dried under vacuum at 80℃ for 10 h to obtain the final product.

[0082] The average particle size of titanium dioxide is 12 nm.

[0083] The waterborne polyurethane emulsion has a solid content of 40%, a viscosity of 1500 mPa·s, and a temperature condition of 25℃. It is product model 2606 purchased from Covestro Polymers (China) Co., Ltd.

[0084] Cellulose ether ⅠⅠ is hydroxypropyl methylcellulose ether; dispersant ⅠⅠ is polycarboxylic acid ammonium salt, purchased from Nippon Nopco Co., Ltd., model SN-5027; wetting agent ⅠⅠ is polysorbate 80; film-forming aid ⅠⅠ is hexadecyl acetate; rheology modifier ⅠⅠ is Dow Chemical (Shanghai) Co., Ltd., model 8W polyurethane rheology modifier.

[0085] The reflective heat-insulating pigment in the reflective heat-insulating color paste and reflective heat-insulating composite rock chip raw materials is titanium dioxide W800.

[0086] The base paint, by weight percentage, consists of: 49.5% water-based acrylic emulsion, 0.26% pH adjuster, 0.27% bactericide and mildew inhibitor, 1.8% polysiloxane, 0.3% defoamer, 0.8% cellulose ether ⅠⅠⅠ, 2.8% film-forming aid ⅠⅠⅠ, 0.35% rheology modifier ⅠⅠⅠ, 0.4% antifreeze, 1.4% modifying agent, and deionized water to make up the balance.

[0087] Cellulose ether ⅠⅠⅠ is hydroxyethyl methyl cellulose ether; film-forming aid ⅠⅠⅠ is propylene glycol phenyl ether; rheology modifier ⅠⅠⅠ is sodium polyacrylate.

[0088] The antifreeze is a combination of diethylene glycol and propylene glycol in a mass ratio of 4.5:1.2.

[0089] The preparation method of the modified additive specifically includes the following steps, by weight: S1: Add 150 parts of deionized water to a high-speed stirrer, stir at room temperature for 6 minutes at 1000 rpm to ensure a suitable water temperature, add 28.8 parts of octamethylcyclotetrasiloxane, heat to 60℃, and stir at 500 rpm for 30 minutes; S2: After stirring, add 18.2 parts of aminopropyltriethoxysilane and 5.5 parts of sodium dodecyl sulfate sequentially, adding 500 parts each time. Stir at rpm for 15 min, then add 8.8 parts of γ-methacryloxypropyltrimethoxysilane, 6.2 parts of isobornyl acrylate and 6.8 parts of glycidyl methacrylate in sequence and continue stirring for 30 min. After stirring, heat to 85℃, add 0.08 parts of benzoyl peroxide, and keep the reaction at this temperature for 4 h; S3: After the reaction is complete, slowly add ammonia water to control the pH of the system to 7.8, then let it cool naturally to room temperature. Filter the product through a 550 mesh sieve and wash with ethanol. The product is then obtained.

[0090] The solid content of the water-based acrylic emulsion in the reflective heat-insulating composite rock sheet and base paint raw materials is 48%, the viscosity is 2500 mPa·s, the temperature condition is 25℃, and the product is RS-706T model purchased from Jiangsu Badefu Technology Development Co., Ltd. in China.

[0091] The defoamer in the reflective heat-insulating color paste, reflective heat-insulating composite rock chips, and base paint raw materials is organosilicon defoamer BYK-066N.

[0092] Sodium hydroxide is used as the pH adjuster in the reflective heat-insulating composite rock sheets and base paint raw materials.

[0093] The bactericide and mildew inhibitor in the reflective heat-insulating composite rock sheets and base paint raw materials is isothiazolinone.

[0094] The polysiloxane in the reflective heat-insulating color paste, reflective heat-insulating composite rock sheet, and base paint raw materials is hydroxyl-terminated polydimethylsiloxane, purchased from Wuhan Smike Biotechnology Co., Ltd., China.

[0095] The colored sand is reflective and heat-insulating colored sand, purchased from Jiangsu Licai Sand New Material Co., Ltd., China, specifically the pink and white 80-120 model product.

[0096] The second aspect of this application provides a method for preparing the above-mentioned reflective heat-insulating rock-flake real stone paint, specifically including the following steps: S1: The reflective heat-insulating color paste raw material is stirred at 1200 rpm for 50 min in a high-speed mixing kettle until it is evenly dispersed. Then, it is ground in a sand mill and passed through a 500-mesh sieve to remove large particles, thus obtaining the reflective heat-insulating color paste; S2: The reflective heat-insulating composite rock flake raw material is stirred at 1500 rpm for 45 min in a high-speed mixing kettle until it is evenly dispersed. Then, it is ground in a sand mill to obtain an intermediate. The intermediate and the reflective heat-insulating color paste are mixed and stirred to create color. Then, the reflective heat-insulating composite rock flakes after coloring with the reflective heat-insulating color paste are obtained through coating, drying, crushing, and sieving processes; S3: The raw material of the base paint is stirred at 1300 rpm for 55 min in a high-speed mixing kettle until it is evenly dispersed, thus obtaining the base paint. Finally, the reflective heat-insulating composite rock flakes after coloring with the reflective heat-insulating color paste, the base paint, and the colored sand are stirred at 700 rpm in a high-speed mixing kettle until they are evenly dispersed and the paint is uniform without stratification, thus obtaining the final product.

[0097] Example 2

[0098] The specific implementation method of this embodiment is basically the same as that of embodiment 1, except that: the reflective heat-insulating rock chip real stone paint, by mass percentage, consists of: 2.5% reflective heat-insulating color paste, 9.5% reflective heat-insulating composite rock chips, 26.5% base paint, and colored sand to make up the balance.

[0099] Example 3

[0100] The specific implementation method of this embodiment is basically the same as that of Embodiment 1, except that: the reflective heat-insulating composite rock sheet, by mass percentage, contains: 9.2% reflective heat-insulating pigment, 10.5% aluminum silicate, 24.6% composite solid material, 33.5% waterborne acrylic emulsion, 8.6% waterborne polyurethane emulsion, 0.36% cellulose ether ⅠⅠ, 0.42% dispersant ⅠⅠ, 0.2% wetting agent ⅠⅠ, 0.24% pH adjuster, 0.3% defoamer, 0.38% bactericide and mildew inhibitor, 0.65% polysiloxane, 1.5% film-forming aid ⅠⅠ, 0.3% rheology modifier ⅠⅠ, with deionized water to make up the balance.

[0101] The composite solid material is a combination of talc powder, heavy calcium carbonate and modified titanium-based particles, with a mass ratio of 10:10:8.

[0102] The average particle size of talc is 2 μm; the average particle size of heavy calcium carbonate is 1.5 μm.

[0103] Comparative Example 1

[0104] The specific implementation method of this comparative example is basically the same as that of Example 1, except that: the reflective heat-insulating rock chip real stone paint, by mass percentage, consists of: 5.5% reflective heat-insulating color paste, 4.5% reflective heat-insulating composite rock chips, 35.5% base paint, and the remaining amount of colored sand.

[0105] Comparative Example 2

[0106] The specific implementation method of this comparative example is basically the same as that of Example 1, except that: the base paint, by mass percentage, consists of: 55.5% water-based acrylic emulsion, 0.26% pH adjuster, 0.27% bactericide and mildew inhibitor, 1.8% polysiloxane, 0.3% defoamer, 0.8% cellulose ether ⅠⅠⅠ, 2.8% film-forming aid ⅠⅠⅠ, 0.35% rheology modifier ⅠⅠⅠ, 0.4% antifreeze, 0.3% modifying agent, and deionized water to make up the balance.

[0107] Comparative Example 3

[0108] The specific implementation method of this comparative example is basically the same as that of Example 1, except that: in the reflective heat-insulating composite rock sheet, the composite solid material is a combination of talc powder, heavy calcium carbonate and modified titanium-based particles, and the mass ratio of the three is 20:15:2.

[0109] Comparative Example 4

[0110] The specific implementation method of this comparative example is basically the same as that of Example 1, except that the preparation method of modified titanium-based particles in the reflective heat-insulating composite rock sheet specifically includes the following steps, by mass: S1: 2 parts of titanium dioxide, 0.35 parts of succinic anhydride and 0.08 parts of γ-aminopropylmethyldiethoxysilane are mixed and added to 60 parts of N,N-dimethylformamide solvent, ultrasonically dispersed at 420W for 3 min, then heated to 68℃, ultrasonically kept at that temperature for 2.2 h, then centrifuged and filtered, washed with ethanol and dried to obtain pretreated particles; S2: 1.4 ... Pretreated particles, 2.6 parts tetrabutyl titanate and 2.4 parts 1,4-naphthalenedicarboxylic acid were mixed and added to 120 parts N,N-dimethylacetamide solvent. The mixture was heated to 60℃ and ultrasonically dispersed at 450W for 30 min. Then, the temperature was raised to 90℃ and kept at that temperature for 5.5 h. Then, 0.5 parts p-aminobenzoic acid and 0.8 parts hydrofluoric acid were added and the temperature was raised to 120℃ and kept at that temperature for 15 h. S3: After the reaction was completed, the mixture was cooled to room temperature, centrifuged and filtered to obtain a solid product. The solid product was washed twice with N,N-dimethylformamide and deionized water, and then dried under vacuum at 80℃ for 10 h to obtain the final product.

[0111] Comparative Example 5

[0112] The specific implementation method of this comparative example is basically the same as that of Example 1, except that the preparation method of the modified titanium-based particles specifically includes the following steps, in parts by mass: S1: 0.8 parts of titanium dioxide, 0.8 parts of zinc oxide, 0.35 parts of succinic anhydride and 0.08 parts of γ-aminopropylmethyldiethoxysilane are mixed and added to 60 parts of N,N-dimethylformamide solvent, ultrasonically dispersed at 420W for 30 min, then heated to 68℃, ultrasonically kept at this temperature for 2.2 h, then centrifuged and filtered, washed with ethanol and dried to obtain pretreated particles; S2: 2.4 parts of the pretreated particles 2.6 parts of tetrabutyl titanate and 1.8 parts of 1,4-naphthalenedicarboxylic acid were mixed and added to 120 parts of N,N-dimethylacetamide solvent. The mixture was heated to 60℃ and ultrasonically dispersed at 450W for 30 min. Then, the temperature was raised to 90℃ and the reaction was maintained for 5.5 h. Then, 1.5 parts of 2-methylimidazole, 0.2 parts of p-aminobenzoic acid and 0.8 parts of hydrofluoric acid were added and the temperature was raised to 120℃ and the reaction was maintained for 15 h. S3: After the reaction was completed, the mixture was cooled to room temperature, centrifuged and filtered to obtain a solid product. The solid product was washed twice with N,N-dimethylformamide and deionized water. Then, it was vacuum dried at 80℃ for 10 h to obtain the final product.

[0113] Comparative Example 6

[0114] The specific implementation method of this comparative example is basically the same as that of Example 1, except that the preparation method of the modified additive specifically includes the following steps, in parts by mass: S1: Add 150 parts of deionized water to a high-speed stirrer, stir at room temperature for 6 minutes at 1000 rpm to ensure the water temperature is suitable, add 28.8 parts of octamethylcyclotetrasiloxane, heat to 60°C, and stir at 500 rpm for 30 minutes; S2: After stirring, add 18.2 parts of aminopropyltriethoxysilane and 5.5 parts of sodium dodecyl sulfate in sequence, adding 500 parts each time. Stir at rpm for 15 min, then add 2.2 parts of γ-methacryloxypropyltrimethoxysilane, 3.3 parts of isobornyl acrylate and 1.5 parts of glycidyl methacrylate in sequence and continue stirring for 30 min. After stirring, heat to 85℃, add 0.08 parts of benzoyl peroxide, and keep the reaction at this temperature for 3.5 h; S3: After the reaction is complete, slowly add ammonia water to control the pH of the system to 7.8, then cool naturally to room temperature. Filter the product through a 550 mesh sieve and wash with ethanol. The product is then obtained.

[0115] Comparative Example 7

[0116] The specific implementation method of this comparative example is basically the same as that of Example 1, except that the preparation method of the modified additive specifically includes the following steps, in parts by mass: S1: Add 150 parts of deionized water to a high-speed stirrer, stir at room temperature for 6 minutes at 1000 rpm to ensure the water temperature is suitable, add 8.5 parts of octamethylcyclotetrasiloxane, heat to 60°C, and stir at 500 rpm for 30 minutes; S2: After stirring, add 18.2 parts of aminopropyltriethoxysilane and 5.5 parts of sodium dodecyl sulfate in sequence, adding 500 parts each time. Stir at rpm for 15 min, then add 15.5 parts of γ-methacryloxypropyltrimethoxysilane, 9.2 parts of isobornyl acrylate and 10.6 parts of glycidyl methacrylate in sequence and continue stirring for 30 min. After stirring, heat to 85℃, add 0.08 parts of benzoyl peroxide, and keep the reaction at this temperature for 3.5 h; S3: After the reaction is complete, slowly add ammonia water to control the pH of the system to 7.8, then cool naturally to room temperature. Filter the product through a 550 mesh sieve and wash with ethanol. The product is then obtained.

[0117] Performance Evaluation

[0118] Solar reflectance test: The solar reflectance of the products prepared in the examples and comparative examples was tested in accordance with the standard JG / T 235-2014. The average value of 10 tests was recorded in Table 1.

[0119] Near-infrared reflectance test: The near-infrared reflectance of the products prepared in the examples and comparative examples was tested in accordance with the standard JG / T 235-2014. The average value of 10 tests was recorded in Table 1.

[0120] Water absorption test: The water absorption of the products prepared in the examples and comparative examples was tested in accordance with the standard JG / T 24-2018. The soaking time was 24 hours, the soaking medium was distilled water, and the temperature was 23±2℃. The test value was the average of 10 tests and recorded in Table 1.

[0121] Stain resistance test: The stain resistance of the products prepared in the examples and comparative examples was tested in accordance with the standard JG / T 24-2018, and the test rating results were recorded in Table 1.

[0122]

[0123] From the embodiments and comparative examples of this application, as well as the data results in Table 1, it can be seen that embodiments 1-3 of this application have significant advantages over comparative examples 1-7 in terms of reflective heat insulation performance, hydrophobic performance, and stain resistance. This is mainly because the modified titanium-based particles with the best performance and the modified additives with the best compound combination used in the embodiments can achieve the repulsion effect on water molecules inside the stone paint through the siloxane and acrylate long chains and corresponding groups contained therein, reducing the water penetration rate and increasing the penetration resistance. On the other hand, it is easier to form a barrier film layer. The presence of this film layer can achieve the barrier effect on water molecules in the system, reduce the system humidity, and the more robust multi-layer cross-linked network it forms can form micro-chemical bonds with other raw materials of the stone paint, fully increasing the mutual adhesion between molecular chains. Thus, during use, it greatly improves the resistance of the stone paint system to molecular chain slippage, enhances the overall toughness and mechanical properties, reduces the breakage phenomenon caused by molecular chain slippage, thereby ensuring the crack resistance and peeling resistance of the stone paint and ensuring the stability of the reflective heat insulation performance.

Claims

1. A reflective and heat-insulating rock-chip paint, characterized in that: By weight percentage, the raw materials of rock chip real stone paint are: 1-8% reflective heat insulation color paste, 5-15% reflective heat insulation composite rock chips, 20-35% base paint, and colored sand to make up the balance. The raw materials for the reflective heat-insulating color paste include: 20-30% reflective heat-insulating pigment; The raw materials for the reflective heat-insulating composite rock sheet include: 6-10% reflective heat-insulating pigment, 10-12% aluminum silicate, and 20-30% composite solid material; The composite solid material is a composition of talc powder, heavy calcium carbonate and modified titanium-based particles, with a mass ratio of (6~10):(10~15):(8~14). The raw materials for the base paint include: 48-50% water-based acrylic emulsion and 0.5-1.5% modifying additives; The method for preparing the modified titanium-based particles includes: S1: mixing titanium dioxide, zinc oxide, succinic anhydride, and γ-aminopropylmethyldiethoxysilane and adding them to N,N-dimethylformamide solvent to obtain pretreated particles; S2: mixing the pretreated particles, tetrabutyl titanate, and 1,4-naphthalenedicarboxylic acid and adding them to N,N-dimethylacetamide solvent, adding 2-methylimidazole, p-aminobenzoic acid, and hydrofluoric acid to continue the reaction; S3: cooling after the reaction is complete, centrifuging and filtering to obtain a solid product, washing, and vacuum drying to obtain the final product; The average particle size of the titanium dioxide is 10~15nm; the mass ratio of the titanium dioxide, zinc oxide, succinic anhydride and γ-aminopropylmethyldiethoxysilane is (1~1.2):(0.1~0.2):(0.3~0.4):(0.05~0.1). The pretreated particles, in a mass ratio of tetrabutyl titanate, 1,4-naphthalenedicarboxylic acid, 2-methylimidazole, and p-aminobenzoic acid, are (1.2~1.5):(2.5~3):(2.2~2.6):(0.3~0.5):(0.4~0.6). The preparation method of the modified additive includes: S1: Adding octamethylcyclotetrasiloxane to deionized water and heating and stirring; S2: After stirring, adding aminopropyltriethoxysilane, sodium dodecyl sulfate, γ-methacryloyloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate in sequence, stirring and reacting, adding benzoyl peroxide, and continuing the reaction at a constant temperature; S3: After the reaction is complete, slowly adding ammonia water, controlling the pH value of the system to 7.5~8, cooling, sieving the product, washing, and obtaining the product. The mass ratio of the octamethylcyclotetrasiloxane, aminopropyltriethoxysilane and sodium dodecyl sulfate is (25~30):(15~20):(5~6); The mass ratio of octamethylcyclotetrasiloxane, γ-methacryloyloxypropyltrimethoxysilane, isobornyl acrylate and glycidyl methacrylate is (25~30):(7~10):(5~8):(5~8); The mass ratio of the reflective heat-insulating color paste, the reflective heat-insulating composite rock sheet and the base paint is (2~5):(5~10):(25~30). The reflective heat-insulating color paste, by mass percentage, also includes: dispersant I 3~5%, wetting agent I 1.5~2.5%, cellulose ether I 1~3%, defoamer 0.5~0.8%, film-forming aid I 2~2.5%, rheology modifier I 0.3~0.5%, and deionized water to make up the balance; The talc powder has an average particle size of 1.5~2μm; the heavy calcium carbonate has an average particle size of 0.5~1.5μm. The dispersant I is polyvinylpyrrolidone or a polycarboxylate; the wetting agent I is ethylene bis-stearamide or polyoxyethylene glycerol tristearate; the cellulose ether I is at least one of hydroxyethyl cellulose ether, hydroxypropyl cellulose ether, and hydroxyethyl methyl cellulose ether; and / or, the film-forming aid I is at least one of dodecyl alcohol ester, hexadecyl alcohol ester, and sorbitan tristearate; the rheology modifier I is organically modified bentonite or sodium polyacrylate; The reflective heat-insulating composite rock sheet, by mass percentage, further comprises: 30-35% waterborne acrylic emulsion, 8-10% waterborne polyurethane emulsion, 0.2-0.5% cellulose ether ⅠⅠ, 0.3-0.6% dispersant ⅠⅠ, 0.1-0.2% wetting agent ⅠⅠ, 0.2-0.3% pH adjuster, 0.3-0.7% defoamer, 0.3-0.5% bactericide and mildew inhibitor, 0.5-1% polysiloxane, 1-2% film-forming aid ⅠⅠ, 0.1-0.3% rheology modifier ⅠⅠ, with deionized water to make up the balance; and / or, the base paint, by mass percentage, further comprises: 0.2-0.3% pH adjuster, 0.2-0.5% bactericide and mildew inhibitor, 1-2% polysiloxane, 0.2-0.5% defoamer, 0.6-1% cellulose ether ⅠⅠⅠ, and film-forming aid ⅠⅠⅠ. 2.5~3%, rheology modifier IⅠⅠⅠ 0.1~0.5%, antifreeze 0.2~0.5%, deionized water to make up the balance; The reflective heat-insulating pigments in the reflective heat-insulating color paste and reflective heat-insulating composite rock chip raw materials are at least one of titanium dioxide W800, iron oxide yellow, cobalt green, cobalt blue, titanium nickel yellow, zinc iron yellow and chrome iron black.

2. A method for preparing the reflective and heat-insulating rock-slice real stone paint according to claim 1, characterized in that: Specifically, the following steps are included: S1: The reflective heat-insulating color paste raw material is mixed in a high-speed mixing tank at 1000-1500 rpm for 40-60 minutes until it is evenly dispersed. Then, it is ground in a sand mill and passed through a 400-500 mesh sieve to remove large particles, obtaining the reflective heat-insulating color paste. S2: The reflective heat-insulating composite rock chip raw material is mixed in a high-speed mixing tank at 1000-1500 rpm for 35-45 minutes until it is evenly dispersed. Then, it is ground in a sand mill to obtain an intermediate. The intermediate and reflective heat-insulating... The color paste is mixed and stirred to create color, and then coated, dried, crushed and sieved to obtain reflective heat-insulating composite rock sheets after coloring with reflective heat-insulating color paste; S3: The raw materials of the base paint are stirred in a high-speed mixing kettle at 1000~1500rpm for 40~60min until they are evenly dispersed to obtain the base paint. Finally, the reflective heat-insulating composite rock sheets after coloring with reflective heat-insulating color paste, the base paint and colored sand are stirred in a high-speed mixing kettle at 600~800rpm until they are evenly dispersed and the paint is uniform without layering.

3. The application of the reflective heat-insulating rock chip real stone paint according to claim 1 in commercial building exterior wall coatings, residential building exterior wall coatings, industrial plant exterior wall coatings, and cold storage building exterior wall coatings.

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