A water-based fluorescent architectural coating composition

Abstract

This invention provides a water-based architectural fluorescent coating composition, using Eu as the primary component. 3+ Ions were used to prepare hexagonal micro / nanosheet europium-zinc ammonium phosphate particles as red phosphors. The material can be highly dispersed in silicone-acrylic emulsion. Using europium-zinc ammonium phosphate fluorescent components as pigments and aqueous silicone-acrylic emulsion as film-forming substances, corrosion-resistant, wear-resistant, and aqueous silicone-acrylic emulsion luminescent coatings were prepared.

Description

Technical Field

[0001] This invention belongs to the field of coating technology and relates to a water-based fluorescent architectural coating composition, which can be widely used in fields requiring bright and vivid colors, such as highways, railways, road signs, artificial landscapes, advertising signs, safety signs, traffic guardrails, underground parking lots, dance hall decoration, architectural decoration, fishing gear, etc. Background Technology

[0002] With the development of the building decoration industry, the coatings industry has also developed accordingly, and various functional coatings have appeared on the market, including fluorescent coatings. Rare earth luminescent materials, for example, are produced using rare earth elements, which belong to Group IIIB of the periodic table. These rare earth elements include scandium (Sc), yttrium (Y), and 15 lanthanide elements. Their similar atomic structures and ionic radii allow rare earth elements to substitute for each other at lattice sites, resulting in richer compound structures and wider applications.

[0003] The luminescence of rare earth ions mainly consists of two transitions: 4f→4f and 5d→4f. These transitions are primarily influenced by electric dipole interactions. According to spectral selection rules, electric dipole transitions are generally forbidden, but they are extremely sensitive to the symmetry of the crystal field. When the symmetry of the crystal field containing the rare earth ion deviates, this transition is permitted. Because the 4f-shell electrons are protected by the outer shell electrons and are not affected by the external crystal field, the spectral characteristics of the 4f→4f transition are mainly determined by the properties of the rare earth ion itself.

[0004] Among the lanthanides, europium (Eu) has the electron shell [Xe]4f. 7 6s 2 Eu is formed by losing the two outermost electrons and one electron from the penultimate shell. 3+ Ions. Because their crystal field environment is shielded by the outermost electrons, the effect on the 4f electron layer is slight; therefore, in Eu... 3+ In ions, the emission spectrum mainly consists of sharp line peaks from 4f→4f transitions, which appear as follows in the spectrum: 5 D0→ 7 F J Energy level transitions (J=0, 1, 2, 3, 4, 5, 6). Crystal field pair 5 The D0 level has a relatively small impact and cannot cause it to split, but it is significantly affected. 7 F J Energy levels are prone to splitting, and the number of splits in the F level increases with... 7 F J The symmetry of the lattice sites occupied by the energy levels decreases and their number increases. This is due to the Eu level. 3+ It is extremely sensitive to its crystal environment, so even slight changes in the environment can alter its transitions. When Eu 3+ When the ion is in a crystal lattice site with inversion symmetry, the orange magnetic dipole transition (5 D0→ 7 F1) Dominant Eu 3+ Emission of ions. When Eu3+ ions are in a non-inversion symmetric crystal lattice site, red electric dipole transitions dominate Eu3+ ion emission. 3+ The emission and transition of ions can very sensitively detect the signal of parity-selectivity prohibition being broken, and are also known as "hypersensitive transitions". Therefore, in most Eu... 3+ In the luminescence of ions, transition-driven emission accounts for the majority, Eu 3+ Eu ions typically emit red light. High color purity, a sharp, linear emission spectrum, and sensitivity to the crystal lattice make Eu ions... 3+ It is extremely popular among rare earth luminescent ions.

[0005] For example, CN101215470A discloses a europium-doped zinc ammonium phosphate orange-red luminescent powder material and its preparation method, published by Tongji University. This method employs a solvothermal reaction, controlling the synthesis of the zinc ammonium phosphate matrix by controlling the solvent, and using different surfactants to control the morphology of the product. By rationally controlling the reaction temperature, time, and other conditions, the orange-red luminescent material is obtained. The provided preparation method is simple, easy to implement, highly operable, controllable, and quantitative, and the resulting product exhibits good luminescent properties. The product obtained by this method has a regular morphology, and its morphology and luminescent properties show regular changes with changes in solvent and surfactant. The obtained product can be widely used in energy-saving fluorescent lamps, luminescent coatings, and other fields. While the solvothermal method effectively controls the product particle size and prepares high-purity phases, it requires high-temperature and high-pressure resistant synthesis equipment and a large amount of solvent templates, increasing product costs and complicating the process, which is not conducive to large-scale production.

[0006] For example, CN102775987B discloses a method for synthesizing manganese ion-doped zinc phosphate luminescent nanorods. Appropriate amounts of zinc nitrate and manganese nitrate are dissolved in deionized water to form a nitrate mixed solution. An appropriate amount of diammonium hydrogen phosphate solid is prepared into a 0.1 mol / L aqueous solution and added dropwise to the above nitrate mixed solution to form a suspension. The suspension is heated to 70℃, the pH is adjusted to 1-2, and rapid stirring is continued for 12 hours. The resulting precipitate is washed with ethanol and distilled water, centrifuged, and the precipitate is naturally dried at room temperature for 18-36 hours and then heat-treated at 600-1000℃ to obtain manganese ion-doped zinc phosphate nanorod crystals with a diameter of 50-100 nm and a length of 200-500 nm, exhibiting long afterglow luminescence.

[0007] For example, CN106243869B, Shanghai Beta Architectural Technology Co., Ltd., describes a sand-textured fluorescent water-based coating and its preparation method. The fluorescent coating comprises resin-coated fluorescent sand, wherein the resin-coated fluorescent sand is prepared from the following components: 30-60 mesh snowflake-white natural colored sand, resin adhesive, and fluorescent pigment. By coating the fluorescent pigment onto the surface of the sand, the instability of fluorescent pigments in water is solved, while simultaneously enhancing the wall decoration effect of the sand-textured coating, creating a three-dimensional fluorescent coating effect.

[0008] For example, CN107746708B discloses a red long-afterglow phosphor and its preparation method, aiming to provide a phosphor material with red long-afterglow luminescence properties, belonging to the field of phosphor technology. The general chemical formula of this phosphor is Sr. 3-x-y SiAlO5Cl3:xEu 2+ ,yRe 3+ Where Re is one or more combinations of Dy, Gd, and Nd, and the values ​​of x and y are in the ranges of 0.01≤x≤0.05 and 0.01≤y≤0.10, respectively. The luminescent center of this phosphor is Eu. 2+ Ions, through the introduction of Dy 3+ Gd 3+ and Nd 3+ Rare earth impurity ions can effectively enhance its long afterglow effect. The long afterglow phosphor provided by this invention has the characteristics of good chemical stability, high afterglow brightness, and long afterglow time, and can be used in decoration, emergency display and other fields.

[0009] For example, CN113025107B discloses a method for preparing a cuprous iodide-based hybrid fluorescent coating and its application. Cuprous iodide-based luminescent clusters are chemically bonded into the hybrid coating material, synthesizing an organic-inorganic hybrid functional coating with stable luminescent properties based on cuprous iodide clusters. The resulting hybrid fluorescent coating has many advantages, including simple preparation method and film-forming process, low cost, stable fluorescence performance, and large-scale production capability. It also provides corrosion protection and can be applied to decorative coatings via spin coating or blade coating. Furthermore, it can be applied to anti-counterfeiting and other fields using printing technology. This invention not only has significant scientific research value but also commercial potential and broad development prospects. Summary of the Invention

[0010] Based on the above understanding, this invention selects Eu 3+Ions were used as activators in the preparation of red phosphors to develop high-performance fluorescent coatings, specifically europium-zinc ammonium phosphate particles. Using [Rmim]BF4 ionic liquid as the electrolyte, zinc ions were provided through anodic dissolution. The cathode deposition of zinc ions was reduced by switching the power supply between the cathode and anode, forming a saturated Eu-doped zinc ammonium phosphate precursor in the electrolyte. The ionic liquid and aqueous solution were then separated by cooling to obtain a supersaturated precursor solution. Microwave synthesis was performed on the aqueous solution to obtain europium-zinc ammonium phosphate fluorescent components with a 200-400 nm micro-nano hexagonal sheet structure, which could be highly dispersed in a silicone-acrylic emulsion. Using the europium-zinc ammonium phosphate fluorescent component as a pigment and an aqueous silicone-acrylic emulsion as the film-forming material, an aqueous...

[0011] Silicone-acrylic emulsion luminescent coating.

[0012] Specifically: A water-based architectural fluorescent coating composition is made from the following raw materials in parts by weight:

[0013] 40-50 parts silicone-acrylic emulsion, 25-30 parts 200-400nm europium-zinc ammonium phosphate particles, 5-10 parts 6-7μm talc powder, 5-10 parts 3-4μm kaolin, 0.8-1.2 parts BASF Tamol dispersant, 0.5-0.7 parts Huntsman PTF thickener, 0.3-0.5 parts SN-318 defoamer, 2-4 parts ethylene glycol diether or ester alcohol dodecyl film-forming aid, and 15-25 parts water.

[0014] A method for preparing a water-based fluorescent architectural coating includes the following steps:

[0015] (1) Add water to the high-speed dispersion tank, and add BASF Tamol dispersant and part of SN-318 defoamer in sequence under stirring conditions of 400-500 rpm, and continue stirring for 1-2 min;

[0016] (2) Increase the rotation speed to 1200-1400 rpm, and add 6-7 μm talc, 3-4 μm kaolin and 200-400 nm europium-zinc ammonium phosphate particles in sequence, and continue stirring for 10-20 min;

[0017] (3) Adjust the speed to 800-1000 rpm, add silicone acrylic emulsion, film-forming aid, Huntsman PTF thickener and the remaining defoamer in sequence, stir continuously for 10-20 minutes, stop stirring, let stand, filter to obtain the desired coating.

[0018] The europium-zinc ammonium phosphate particles are prepared by the following steps:

[0019] (1) Fluoroboric acid and chloro-1-alkyl-3-methylimidazolium were stirred at 42°C for 12 h at a mass ratio of 1:3 and mixed evenly. The organic layer was extracted with chloromethane and the ionic liquid [Rmim]BF4 was obtained by vacuum rotary evaporation.

[0020] (1) Under an inert atmosphere, heat 200 mL of ionic liquid [Rmim]BF4 at 70-80℃ for 20-30 min, then slowly add 100 mL of deionized water, 1.5-2.2 g of Eu(NO3)3·6H2O and 5-6 g of ammonium dihydrogen phosphate, and mechanically stir and ultrasonically stir for 30-40 min to obtain the ionic liquid electrolyte;

[0021] (2) Using high-purity zinc as the working electrode and platinum sheet as the counter electrode, insert it into the above electrolyte, and then perform electrolysis under an inert atmosphere. Control the temperature at 70-80℃. Use a switchable DC power supply. Use high-purity zinc as the anode and platinum sheet as the cathode. The voltage is 4-5V and the time is 3-5min. Switch the current direction. Use high-purity zinc as the cathode and platinum sheet as the anode. The voltage is 1-2V and the time is 0.5-1min. The electrolysis cycle is 15-20 times.

[0022] (3) Remove the electrolyte, stir continuously at 100-200 rpm for 10-15 min, cool to 2-3℃, keep at constant temperature for 24 h, separate into layers, and take the supernatant;

[0023] (4) Place the liquid in a microwave reactor for microwave treatment. Microwave treatment conditions: stirring at 80-100 rpm, microwave power of 240-480W, time of 20-30 min, and then cool naturally. Centrifuge and filter the microwave-treated liquid. Wash the solid with deionized water and ethanol in sequence, and then dry it under vacuum to obtain europium-zinc ammonium phosphate particles.

[0024] Beneficial technical effects: (1) The europium-zinc ammonium phosphate fluorescent particles prepared by this invention have good dispersibility, compatibility, and weather resistance in the coating emulsion, especially the excellent wear resistance and corrosion resistance of the coating; (2) Zinc ions are slowly provided by anodic dissolution, and the zinc ions are free in the aqueous solution of the ionic liquid [Rmim]BF4. Then, the precursor of europium-zinc ammonium phosphate is forced into the aqueous solution by cooling to form a supersaturated solution. Then, hexagonal sheet-like micro-nano europium-zinc ammonium phosphate fluorescent particles are obtained by microwave treatment, such as Figure 1 As shown, the fluorescent particles have high color rendering properties; (3) The power supply control affects the doping effect or doping amount of rare earth europium in zinc ammonium phosphate, which directly affects the intensity of emitted light and excitation light, and ultimately affects the red light effect of the fluorescent coating; (4) By controlling the morphology and purity of europium-zinc ammonium phosphate crystals through electrolysis, the luminescence performance of the red fluorescent material is significantly enhanced. Attached Figure Description

[0025] Appendix Figure 1 Europium-zinc ammonium phosphate particles prepared in Example 2 of this invention.

[0026] Appendix Figure 2 The excitation spectra (PLE) of Embodiment 2 and Comparative Example 1 of the present invention are shown.

[0027] Appendix Figure 3 The emission spectra (PL) of Embodiment 2 and Comparative Example 1 of the present invention are shown.

[0028] Appendix Figure 4 Color coordinate diagram of the red fluorescent material prepared in Example 2. Detailed Implementation Example 1

[0029] A method for preparing europium-zinc ammonium phosphate particles, comprising the following steps:

[0030] (1) Fluoroboric acid and chloro-1-alkyl-3-methylimidazolium were stirred at 42°C for 12 h at a mass ratio of 1:3 and mixed evenly. The organic layer was extracted with chloromethane and the ionic liquid [Rmim]BF4 was obtained by vacuum rotary evaporation.

[0031] (1) Under an inert atmosphere, 200 mL of ionic liquid [Rmim]BF4 was heated at 70 °C for 20 min, and then 100 mL of deionized water, 1.5 g of Eu(NO3)3·6H2O and 5 g of ammonium dihydrogen phosphate were slowly added. The mixture was mechanically stirred and ultrasonically stirred for 30 min to obtain the ionic liquid electrolyte.

[0032] (2) Using high-purity zinc as the working electrode and platinum sheet as the counter electrode, the electrode is inserted into the electrolyte and then electrolyzed under an inert atmosphere. The temperature is controlled at 70°C and a switchable DC power supply is used. High-purity zinc is used as the anode and platinum sheet as the cathode. The voltage is 4V and the time is 3min. The current direction is switched to high-purity zinc as the cathode and platinum sheet as the anode. The voltage is 1V and the time is 0.5min. The electrolysis cycle is 15 times.

[0033] (3) Drain the electrolyte, stir continuously at 100 rpm for 10 min, cool down to 2℃, keep at constant temperature for 24 h, separate into layers, and take the supernatant;

[0034] (4) Place the liquid in a microwave reactor for microwave treatment. Microwave treatment conditions: stirring at 80 rpm, microwave power of 240 W, time of 20 min, and then cool naturally. Centrifuge and filter the microwave-treated liquid. Wash the solid with deionized water and ethanol in sequence, and then dry it under vacuum to obtain europium-zinc ammonium phosphate particles. Example 2

[0035] A method for preparing europium-zinc ammonium phosphate particles, comprising the following steps:

[0036] (1) Fluoroboric acid and chloro-1-alkyl-3-methylimidazolium were stirred at 42°C for 12 h at a mass ratio of 1:3 and mixed evenly. The organic layer was extracted with chloromethane and the ionic liquid [Rmim]BF4 was obtained by vacuum rotary evaporation.

[0037] (1) Under an inert atmosphere, 200 mL of ionic liquid [Rmim]BF4 was heated at 75 °C for 25 min, and then 100 mL of deionized water, 1.85 g of Eu(NO3)3·6H2O and 5.5 g of ammonium dihydrogen phosphate were slowly added. The mixture was mechanically stirred and ultrasonically stirred for 35 min to obtain the ionic liquid electrolyte.

[0038] (2) Using high-purity zinc as the working electrode and platinum sheet as the counter electrode, the electrode is inserted into the electrolyte and then electrolyzed under an inert atmosphere. The temperature is controlled at 75°C and a switchable DC power supply is used. High-purity zinc is used as the anode and platinum sheet as the cathode. The voltage is 4.5V and the time is 4min. The current direction is switched to high-purity zinc as the cathode and platinum sheet as the anode. The voltage is 1.5V and the time is 0.75min. The electrolysis cycle is 17 times.

[0039] (3) Remove the electrolyte, stir continuously at 150 rpm for 12.5 min, cool down to 2.5℃, keep at a constant temperature for 24 h, separate into layers, and take the supernatant;

[0040] (4) Place the liquid in a microwave reactor for microwave treatment. Microwave treatment conditions: stir at 90 rpm, microwave power at 360 W, time 25 min, and then cool naturally. Centrifuge and filter the microwave-treated liquid. Wash the solid with deionized water and ethanol in sequence, and then dry under vacuum to obtain europium-zinc ammonium phosphate particles. Example 3

[0041] A method for preparing europium-zinc ammonium phosphate particles, comprising the following steps:

[0042] (1) Fluoroboric acid and chloro-1-alkyl-3-methylimidazolium were stirred at 42°C for 12 h at a mass ratio of 1:3 and mixed evenly. The organic layer was extracted with chloromethane and the ionic liquid [Rmim]BF4 was obtained by vacuum rotary evaporation.

[0043] (1) Under an inert atmosphere, 200 mL of ionic liquid [Rmim]BF4 was heated at 80 °C for 30 min, and then 100 mL of deionized water, 2.2 g of Eu(NO3)3·6H2O and 6 g of ammonium dihydrogen phosphate were slowly added. The mixture was mechanically stirred and ultrasonically stirred for 40 min to obtain the ionic liquid electrolyte.

[0044] (2) Using high-purity zinc as the working electrode and platinum sheet as the counter electrode, the electrode is inserted into the electrolyte and then electrolyzed under an inert atmosphere. The temperature is controlled at 80°C and a switchable DC power supply is used. High-purity zinc is used as the anode and platinum sheet as the cathode. The voltage is 5V and the time is 5min. The current direction is switched so that high-purity zinc is used as the cathode and platinum sheet as the anode. The voltage is 2V and the time is 1min. The electrolysis cycle is 20 times.

[0045] (3) Remove the electrolyte, stir continuously at 200 rpm for 15 min, cool to 3℃, keep at constant temperature for 24 h, separate into layers, and take the supernatant;

[0046] (4) Place the liquid in a microwave reactor for microwave treatment. Microwave treatment conditions: 100 rpm stirring, microwave power of 480 W, time of 30 min and natural cooling. Centrifuge and filter the microwave-treated liquid. Wash the solid with deionized water and ethanol in sequence and vacuum dry to obtain europium-zinc ammonium phosphate particles.

[0047] Comparative Example 1: A method for preparing europium-zinc ammonium phosphate particles, which is obtained through the following steps:

[0048] (1) Fluoroboric acid and chloro-1-alkyl-3-methylimidazolium were stirred at 42°C for 12 h at a mass ratio of 1:3 and mixed evenly. The organic layer was extracted with chloromethane and the ionic liquid [Rmim]BF4 was obtained by vacuum rotary evaporation.

[0049] (1) Under an inert atmosphere, 200 mL of ionic liquid [Rmim]BF4 was heated at 75 °C for 25 min, and then 100 mL of deionized water, 1.85 g of Eu(NO3)3·6H2O and 5.5 g of ammonium dihydrogen phosphate were slowly added. The mixture was mechanically stirred and ultrasonically stirred for 35 min to obtain the ionic liquid electrolyte.

[0050] (2) Using high-purity zinc as the working electrode and platinum sheet as the counter electrode, insert it into the above electrolyte and then perform electrolysis under an inert atmosphere. The temperature is controlled at 75°C. A switchable DC power supply is used, with high-purity zinc as the anode and platinum sheet as the cathode. The voltage is 4.5V and the time is 68min.

[0051] (3) Remove the electrolyte, stir continuously at 150 rpm for 12.5 min, cool down to 2.5℃, keep at a constant temperature for 24 h, separate into layers, and take the supernatant;

[0052] (4) Place the liquid in a microwave reactor for microwave treatment. Microwave treatment conditions: stir at 90 rpm, microwave power at 360 W, time 25 min, and then cool naturally. Centrifuge and filter the microwave-treated liquid. Wash the solid with deionized water and ethanol in sequence, and then dry under vacuum to obtain europium-zinc ammonium phosphate particles.

[0053] Excitation spectrum: refers to the variation in intensity of a certain spectral line or band of emission with the wavelength (or frequency) of the excitation light. The excitation spectrum reflects the effect of different wavelengths of light on the material.

[0054] Emission Spectrum: Also known as luminescence spectrum, the emission spectrum of a luminescent material refers to the distribution of emitted energy according to wavelength or frequency, often represented by a curve. Testing of Excitation and Emission Spectral Performance: The excitation and emission spectra of the luminescent powder were measured using a Hitachi F-4500 fluorescence spectrometer. The light source was a 150W xenon lamp, and the monochromator slit width was [missing information].

[0055] 0.5mm, scan step size is 1nm.

[0056] Through append Figure 2 PLE testing showed that the excitation peak range of Example 2 (black line) and Comparative Example 2 (blue line) was 310-570 nm, with the strongest excitation peak at 390 nm. Figure 3 PL testing revealed that the emission spectrum peaks of Example 2 (red) and Comparative Example 2 (blue-green) were mainly concentrated at 590, 614, 651, and 690 nm, respectively, corresponding to... 5 D0 → 7 F1, 5 D0→ 7 F2, 5 D0 → 7 F3, 5 D0 → 7 F4, wherein the emission peak area of ​​Example 2 is 1.42 times that of Example 2, and the prepared near-ultraviolet-excited red phosphor can effectively emit red light when excited at 390 nm. Figure 4 As shown, its CIE color coordinates are in the red light region (x=0.6351, y=0.3409), indicating that the sample has high color rendering properties. Example 4

[0057] A water-based fluorescent architectural coating composition is made from the following raw materials in parts by weight:

[0058] 45 parts of silicone-acrylic emulsion, 28 parts of 200-400nm europium-zinc ammonium phosphate particles prepared in Example 2, 7.5 parts of 6-7μm talc powder, 7.5 parts of 3-4μm kaolin, 1 part of BASF Tamol dispersant, 0.6 parts of Huntsman PTF thickener, 0.4 parts of SN-318 defoamer, 3 parts of ethylene glycol diether or ester alcohol dodecyl film-forming aid, and 20 parts of water.

[0059] Includes the following steps:

[0060] (1) Add water to the high-speed dispersion tank, and add BASF Tamol dispersant and part of SN-318 defoamer in sequence under stirring conditions of 450 rpm, and continue stirring for 1.5 min;

[0061] (2) Increase the rotation speed to 1100 rpm, and add 6-7 μm talc, 3-4 μm kaolin and 200-400 nm europium-zinc ammonium phosphate particles in sequence, and continue stirring for 15 min;

[0062] (3) Adjust the speed to 900 rpm, add silicone acrylic emulsion, film-forming aid, Huntsman PTF thickener and the remaining defoamer in sequence, stir continuously for 15 min, stop stirring, let stand, filter to obtain the desired coating.

[0063] Comparative Example 2, a water-based architectural fluorescent coating composition, is made from the following raw materials in parts by weight:

[0064] 45 parts of silicone-acrylic emulsion, 28 parts of 200-400nm europium-zinc ammonium phosphate particles prepared in Comparative Example 1, 7.5 parts of 6-7μm talc powder, 7.5 parts of 3-4μm kaolin, 1 part of BASF Tamol dispersant, 0.6 parts of Huntsman PTF thickener, 0.4 parts of SN-318 defoamer, 3 parts of ethylene glycol diether or ester alcohol dodecyl film-forming aid, and 20 parts of water.

[0065] Includes the following steps:

[0066] (1) Add water to the high-speed dispersion tank, and add BASF Tamol dispersant and part of SN-318 defoamer in sequence under stirring conditions of 450 rpm, and continue stirring for 1.5 min;

[0067] (2) Increase the rotation speed to 1100 rpm, and add 6-7 μm talc, 3-4 μm kaolin and 200-400 nm europium-zinc ammonium phosphate particles in sequence, and continue stirring for 15 min;

[0068] (3) Adjust the speed to 900 rpm, add silicone acrylic emulsion, film-forming aid, Huntsman PTF thickener and the remaining defoamer in sequence, stir continuously for 15 min, stop stirring, let stand, filter to obtain the desired coating.

[0069] The coatings prepared in Example 4 and Comparative Example 2 were repeatedly sprayed onto the substrate surface. After each spraying, the substrate was immediately dried in a 50°C oven for 0.5 hours, followed by another spraying and drying. The coating thickness was 10 micrometers. The abrasion resistance of each coating was determined according to the measurement method in national standard GB1768-79. The specific operation was as follows: The steel substrate with each coating was fixed on the working turntable of the abrasion tester. A 500g effective load was applied to the pressure arm, and the substrate was polished 500 times at the same rotation speed. The weights were then measured to calculate the wear amount. The wear amount of Example 4 was 0.0083g, and that of Comparative Example 2 was 0.0089g, showing no significant difference in abrasion resistance. The Example 4 showed better abrasion resistance. For corrosion resistance testing, the corrosion potential of Example 4 was -623mV, and the corrosion current density was 2.738*10⁻⁶. -8 The corrosion potential of Comparative Example 3 is -659mV, and the corrosion current density is 13.287*10 A / cm. -8 In terms of A / cm and corrosion resistance, Example 4 is superior, indicating that the fluorescent particles prepared in Example 2 have better dispersibility in the coating or better bonding between the particles and the coating. The emission and excitation spectra of the fluorescent materials in Example 4 and Comparative Example 2 were tested. The main peak positions of the emission and excitation light remained unchanged, only the intensity decreased. Compared to Example 2, Comparative Example 2 showed a loss of approximately 6.3% in emission intensity and approximately 8.9% in excitation intensity. This is mainly because the coating reflected or absorbed some of the incident light, reducing the light energy absorbed by the fluorescent particles and thus weakening the emitted fluorescence.

[0070] The above-described embodiments are merely illustrative of certain implementations of the present invention, and are described in a relatively specific and detailed manner. However, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements are all within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the appended claims.

Claims

1. An aqueous architectural fluorescent coating composition characterized by: The following raw materials are prepared by weight parts: silicone-acrylate emulsion 40-50 parts, 200-400 nm europium-zinc ammonium phosphate particles 25-30 parts, 6-7 μm talc 5-10 parts, 3-4 μm kaolin 5-10 parts, BASF Tamol dispersant 0.8-1.2 parts, Hensmen PTF thickener 0.5-0.7 parts, SN-318 defoaming agent 0.3-0.5 parts, ethylene glycol diether or fatty alcohol dodecane film-forming aid 2-4 parts, water 15-25 parts; The europium-zinc ammonium phosphate particles are prepared by the following steps: (1) Fluoroboric acid and chloro-1-alkyl-3-methyl imidazole are mixed uniformly after stirring at 42°C for 12 h at a mass ratio of 1:3, and the organic layer is extracted using methyl chloride, and an ionic liquid [Rmim]BF4 is obtained using a vacuum rotary evaporator; (2) The ionic liquid [Rmim]BF4 is heated at 70-80°C for 20-30 min under an inert atmosphere, and then deionized water, 1.5-2.2 g of Eu(NO3)3·6H2O, and 5-6 g of ammonium dihydrogen phosphate are slowly added, and mechanical stirring and ultrasonic stirring are performed for 30-40 min to obtain an ionic liquid electrolyte; (3) A high-purity zinc electrode is used as the working electrode, and a platinum sheet is used as the counter electrode, which is inserted into the above electrolyte, and then electrolysis is performed under an inert atmosphere, with the temperature controlled at 70-80°C, a switchable direct current power source is used, with high-purity zinc as the anode and platinum as the cathode, the voltage is 4-5 V, and the time is 3-5 min; the current direction is switched, with high-purity zinc as the cathode and platinum as the anode, the voltage is 1-2 V, and the time is 0.5-1 min; the electrolysis treatment cycle is 15-20 times; (4) The electrolyte is discharged, continuously stirred at 100-200 rpm for 10-15 min, cooled to 1-5°C, and placed at a constant temperature for 24 h, then separated into layers, and the upper liquid is taken; (5) The upper liquid is placed in a microwave reactor for microwave treatment, with the microwave treatment conditions being 80-100 rpm stirring, a microwave power of 240-480 W, and a time of 20-30 min, followed by natural cooling, centrifugation, and filtration of the microwave-treated liquid, and the solid is sequentially washed with deionized water and ethanol, and vacuum dried to obtain europium-zinc ammonium phosphate particles.

2. An aqueous architectural fluorescent coating composition as claimed in claim 1 characterised in that The amount of ionic liquid [Rmim]BF4 used in step (2) is 200 mL, and the amount of deionized water used is 100 mL.

3. An aqueous architectural fluorescent coating composition as claimed in claim 2, characterised in that Cool to 2-3°C.

Images