Self-luminous coating material as well as preparation method and application thereof

Abstract

The invention relates to a self-luminous coating material as well as a preparation method and application thereof, and belongs to the technical field of advanced functional materials. The self-luminous coating material comprises modified noctilucent powder, a resin matrix, an inorganic filler, a light stabilizer, an anti-settling agent, a coalescing agent, a defoaming agent, a flatting agent, a thickening agent, a toughening agent and a dispersing agent, the types and contents of the components of the self-luminous coating material are regulated and controlled, and particularly, SrAl2O4: Eu < 2 + >, Dy < 3 + > and Cu < + > of which the surface is coated with a silicon dioxide layer are adopted. The self-luminous coating material which is high in brightness, long in afterglow, high in adhesive force and resistant to aging is obtained under the synergistic effect of other components by adopting a polyurethane-polymethyl methacrylate triblock copolymer as a resin matrix and taking Mn < 2 + > as modified luminous powder. The method has good application prospects in self-luminous identification systems in the fields of traffic, fire fighting, buildings, industrial facilities and the like, is adaptive to extreme environments, and meets the use requirements of different scenes.

Description

Technical Field

[0001] The present invention relates to a self-luminous coating material, a preparation method and application thereof, and belongs to the technical field of advanced functional materials. Background Art

[0002] Long-afterglow luminescent materials are self-luminous, functional luminescent coatings. As passive optical materials, they play an irreplaceable role in public safety, emergency guidance, and landscape lighting. Their core performance indicators include afterglow duration, initial brightness, environmental stability, and substrate adhesion. As their application scenarios have expanded from traditional power facility signs to diverse fields such as transportation engineering, fire protection systems, and architectural decoration, more stringent cross-domain requirements have been placed on the material's comprehensive performance. These materials must provide continuous visible light guidance for 12 hours or more in the absence of external light sources and maintain stable performance under extreme temperature fluctuations, UV radiation, and mechanical stress.

[0003] However, the existing long afterglow coating system still has key performance shortcomings, which seriously restricts its large-scale engineering application. Although traditional sulfide-based fluorescent materials (such as ZnS:Cu) have initial brightness advantages, their afterglow time is generally less than 4 hours, and sulfur ion migration occurs after exposure to a humid and hot environment, resulting in a brightness decay rate of more than 50%. Ordinary rare earth aluminate systems (such as SrAl2O4:Eu 2+ ,Dy 3+ While the afterglow time is increased to 10-15 hours, its crystal structure is sensitive to UV rays, and its luminous efficiency drops by over 40% after one year of outdoor use, making it difficult to meet the requirements for long-term maintenance-free coating substrates. To increase luminous intensity, existing technologies often use nano-sized phosphors (particle size <5μm). However, these high-surface-area powders tend to agglomerate in the resin matrix, increasing the coating's porosity and reducing adhesion (cross-hatch testing) from 4B to 2B.

[0004] Therefore, there is an urgent need to develop a self-luminous coating material with high brightness, long afterglow, strong adhesion, and aging resistance that can adapt to the needs of multiple fields, solve the key contradictions of the existing material system in engineering applications, and provide innovative solutions for the safe operation and maintenance of smart cities. Summary of the Invention

[0005] In view of this, the present invention provides a self-luminous coating material, a preparation method and application thereof. The present invention optimizes the composition of the coating material to obtain a self-luminous coating material with high brightness, long afterglow, strong adhesion and aging resistance. It has good application prospects in self-luminous identification systems in the fields of transportation, fire protection, construction and industrial facilities, and is adaptable to extreme environments (large temperature difference, corrosion, humidity) to meet the usage requirements of different scenarios.

[0006] The objectives of the present invention are achieved through the following technical solutions.

[0007] A self-luminous coating material, comprising, by weight:

[0008] Modified luminous powder, 30-45 parts, is a rare earth aluminate with a surface coated with a silicon dioxide layer. The chemical formula of the rare earth aluminate is SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ ;

[0009] The resin matrix, 18-25 parts, is a silicone-polyurethane-polymethyl methacrylate triblock copolymer (PDMS-PU-PMMA). It should be noted that a block copolymer is formed by covalently linking two or more polymer segments of different properties, while the block copolymer of the present invention is a polymer material formed by covalently linking three segments of silicone, polyurethane, and polymethyl methacrylate in an orderly manner.

[0010] Inorganic filler, 5-10 parts, such as at least one of fumed silica, aluminum oxide, titanium dioxide, etc.;

[0011] Light stabilizer, 0.5-0.8 parts, at least one phenolic compound;

[0012] 1-1.5 parts of an anti-settling agent, such as at least one of aluminum stearate, zinc stearate, and polyamide wax;

[0013] 1.5-2.5 parts of a film-forming aid, such as at least one of propylene glycol methyl ether acetate, polyvinyl pyrrolidone, and dipropylene glycol methyl ether;

[0014] Defoaming agent, 0.2-0.5 parts, can be selected from at least one of silicone defoaming agent (such as emulsified methyl silicone oil, polyether modified silicone oil), mineral oil defoaming agent, etc.;

[0015] Leveling agent, 0.1-0.3 parts, which can be selected from at least one of polyether modified silicone, fluorocarbon surfactant, etc.;

[0016] Thickener, 0.5-1 part, which can be selected from at least one of polyurethane-modified polyether, hydrophobically modified cellulose (such as HEC), etc.;

[0017] Toughening agent, 0.6-0.9 parts, can be selected from at least one of dibutyl phthalate, triphenyl phosphate, etc.;

[0018] Dispersant, 0.6-0.8 parts, can be selected from at least one of silane coupling agent (such as KH-570, KH-550), polycarboxylate polymer dispersant, etc.

[0019] Furthermore, the particle size of the modified luminous powder is 6-14 μm. More preferably, the modified luminous powder includes two particle sizes: 8±0.5 μm and 12±0.5 μm, and the mass ratio of the modified luminous powder with a particle size of 8±0.5 μm to the modified luminous powder with a particle size of 12±0.5 μm is 55:45-65:35, and more preferably 58:42-62:38.

[0020] Furthermore, Cu in rare earth aluminates \ With Mn 2+ The molar ratio is 1:0.3-1:0.5.

[0021] Furthermore, the thickness of the silicon dioxide layer coated on the surface of the rare earth aluminate is 50-120 nm; more preferably, the specific surface area of ​​the silicon dioxide layer is greater than 200 m 2 / g.

[0022] Furthermore, the inorganic filler is hydroxylated nano-scale fumed silica, and the specific surface area is more preferably 200-300m 2 / g.

[0023] Furthermore, the light stabilizer is 2-(2H-benzotriazole-2-yl)-4,6-di-tert-amylphenol.

[0024] Furthermore, the anti-settling agent is aluminum stearate. More preferably, the inorganic filler is hydroxylated nano-sized fumed silica, and the mass ratio of hydroxylated nano-sized fumed silica to aluminum stearate is 1:0.1-1:0.3.

[0025] A method for preparing a self-luminous coating material comprises the following steps:

[0026] (1) Preparation of modified luminous powder

[0027] SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2\ The powder is immersed in an alkaline solution to form a hydroxylated layer on its surface;

[0028] SrAl2O4:Eu with a hydroxylated layer on the surface 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is dispersed in SiO2 sol, and the pH is adjusted in the range of 2.5-10.5. The reaction is carried out at 20-85℃. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A silicon dioxide layer of desired thickness is formed on the surface of the powder;

[0029] SrAl2O4:Eu coated with a silicon dioxide layer 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is first dried and then calcined at 290-520°C for 3-5 hours to obtain the modified luminous powder;

[0030] (2) The resin matrix and the film-forming aid are mixed evenly to form a uniform emulsion; the dried modified luminous powder, dispersant, and defoaming agent are added to the uniform emulsion, stirred and mixed evenly, and then the inorganic filler, light stabilizer, anti-settling agent, and toughening agent are added, and the stirring and mixing are continued. Finally, the leveling agent and thickener are added, and the stirring and mixing are continued to obtain a self-luminous coating material.

[0031] Furthermore, the unmodified luminous powder SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The preparation method is as follows: SrCO3, Al2O3, Eu2O3, Dy2O3, CuO and MnCO3 are weighed according to the stoichiometric ratio, the weighed raw materials are added to a ball mill for wet ball milling dispersion, and the ball-milled slurry is vacuum dried to obtain a uniformly mixed powder; the mixed powder is placed in a reducing atmosphere, calcined at 1300-1400 ° C for 6-7 hours, and then cooled and crushed and sieved to obtain SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ Powder.

[0032] Furthermore, SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is immersed in an alkali metal hydroxide solution with a concentration of 0.05-0.5 mol / L and immersed at 50-70 ° C for 1-3 hours. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A hydroxylation layer is formed on the surface of the powder.

[0033] Furthermore, the SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+After the powder and SiO2 sol are evenly mixed in a mass ratio of 1:10-1:30, the mixture is first reacted at 20-35°C for 0.5-1.5h in the range of pH = 2.5-3.5 to form an initial SiO2 core layer, and then the pH is adjusted to 6.5-7.5, and the mixture is continued to react at 55-65°C for 1.5-3h to form a SiO2 layer, and then the pH is adjusted to 9.5-10.5, and the mixture is aged at 75-85°C for 3-5h to densify the surface of the SiO2 layer. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A SiO2 layer of desired thickness is formed on the surface of the powder.

[0034] Furthermore, SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The particle size of the powder is 1-5 μm.

[0035] Furthermore, SiO2 sol is prepared by the following method: tetraethyl orthosilicate (TEOS), anhydrous ethanol and deionized water are mixed, and a template agent (such as CTAB, hexadecyltrimethylammonium bromide) and a silane coupling agent (such as KH-570) are added, and HCl is added dropwise to adjust the pH, and then stirred to form a transparent sol, thereby obtaining SiO2 sol;

[0036] Preferably, the volume ratio of tetraethyl orthosilicate (TEOS), anhydrous ethanol and deionized water is (0.8-1.2):(3.5-4.5):(0.4-0.6); the concentration of the template in the reaction system is 0.005-0.02 mol / L; the mass fraction of the silane coupling agent in the reaction system is 0.4-0.6 wt%; and HCl is used to adjust the pH to 3±0.5.

[0037] Furthermore, the resin matrix is ​​prepared by the following method:

[0038] Synthesis of silicone block (PDMS):

[0039] (1) Bis-terminal hydroxypropyl silicone oil (PDMS-OH) and isophorone diisocyanate (IPDI) are mixed in a molar ratio of 1:(2.0-2.5), and a catalyst (such as dibutyltin dilaurate, DBTDL) is added at a mass fraction of 0.05-0.08%. The mixture is reacted at 65-75°C for 2-4 hours under N2 or inert gas protection to generate a PDMS prepolymer containing isocyanate groups at both ends (PDMS-NCO). Hydroxyethyl acrylate (HEA) is then added at a molar ratio of PDMS-NCO:HEA = 1:(1.0-1.4) to cap the ends. The mixture is reacted at 55-65°C for 2-3 hours to obtain an acrylate-terminated silicone block (PDMS-HEA);

[0040] (2) Construction of polyurethane-acrylic resin block (PU-PMMA)

[0041] 2-Cyano-2-propylbenzotrithiocarbonate (CPBT) and toluene are mixed in a volume ratio of 1:(4-6), and bis(1,1′-(1,3,4-oxadiazole-2,5-diyldi-4,1-phenylene)-4-butoxy-2-methylbenzoate)ethylaluminum (EtAl(ODBP)2) is added as a ligand at a concentration of 0.05-0.2 mol / L to form an active RAFT system; the molar ratio of PCL:IPDI:RAFT system is 1:(1.8-2.2). : 1. Add polycaprolactone diol (PCL) and isophorone diisocyanate (IPDI) to a RAFT system and react at 50-60° C. for 4-5 hours to generate a polyurethane prepolymer (PU); add a mixture of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (AM-314) in a molar ratio of (8-10):1 to the PU, heat to 70-80° C. and react for 6-7 hours, and induce crosslinking by intermittent ultraviolet light irradiation to obtain a polyurethane-acrylic resin block (PU-PMMA);

[0042] (3) Triblock copolymer assembly

[0043] PDMS-HEA and PU-PMMA are mixed in a molar ratio of 1:(0.9-1.1), and a silane coupling agent (such as KH570) is added at a mass fraction of 0.5%. After ultrasonic dispersion, a thiol-ene click reaction is carried out by UV irradiation to achieve block covalent connection. After annealing treatment and solvent evaporation, self-assembly is induced to form a layered ordered PDMS-PU-PMMA triblock structure.

[0044] Furthermore, the moisture content of the dried modified luminous powder is not greater than 0.1wt.%, because the moisture content of the modified luminous powder will affect the initial brightness of the coating. If the moisture content of the modified luminous powder is greater than 0.5wt.%, it will cause the initial brightness of the coating to decrease by ≥30%; after adding the dispersant, stirring and mixing is carried out at a temperature below 45°C. This is because when the temperature is high, the silica coating on the surface of the modified luminous powder is easily broken, which will shorten the afterglow time, and the afterglow time can be shortened to ≤12 hours.

[0045] An application of a self-luminous coating material. The self-luminous coating material of the present invention is used to prepare self-luminous signs in the fields of transportation, fire emergency, architectural landscape, and industrial facilities.

[0046] Beneficial effects:

[0047] (1) Compared with traditional binary-doped rare earth aluminates, the quaternary-doped rare earth aluminates used in this application can construct multi-level electron traps, improve the electron capture density, and prolong the afterglow time; at the same time, the surface of the quaternary-doped rare earth aluminates is modified by coating with silicon dioxide, which not only improves its dispersibility and luminous efficiency, but also helps to further reduce the porosity of the coating prepared by the subsequent self-luminous coating material.

[0048] (2) Among the quaternary doped rare earth aluminates used in this application, especially Cu + / Mn 2+ The molar ratio of Mn is the key factor in regulating both the initial brightness and the afterglow time. 2+ Too high a doping concentration will cause the host lattice Sr 2+ Site distortion, reducing the luminescence center Eu 2+ The activation efficiency of Cu + As a shallow trap providing a fast release channel, Mn 2+ As a deep trap to extend the storage time, if the molar ratio of the two is unbalanced, the continuity of the trap energy level will be destroyed, thus affecting the afterglow time. + / Mn 2+ The molar ratio is preferably limited to (1:0.3-0.5), which can make the initial luminous brightness of the modified luminous powder ≥1.8cd / m 2 , afterglow time ≥16 hours (25℃ darkroom environment).

[0049] (3) This application uses two types of modified luminous powder with different particle sizes, mainly to reduce the porosity of the coating through the complementary effect of particle sizes, which can reduce the porosity of the coating to ≤1.2%. In addition, the two particle sizes used in this application have a specific surface area of ​​1.6-2.0m 2 / g range, which can avoid the resin-powder interface defects caused by the excessive specific surface area of ​​nanopowders and effectively solve the dispersion problem.

[0050] (4) This application uses a silicone-polyurethane-polymethyl methacrylate triblock copolymer as the resin matrix, and forms a "rigid and flexible" structure through the copolymerization of three polymer segments. In particular, the PDMS segment can effectively improve the low-temperature crack resistance, and the PMMA segment can significantly improve the mechanical strength, so that the resin matrix has flexibility (-40°C crack resistance), weather resistance and high mechanical strength, meeting the use requirements of different working conditions.

[0051] (5) This application uses aluminum stearate as an anti-settling agent and hydroxylated nano-scale fumed silica as an inorganic filler. The two can form an interpenetrating network through coordination bonds, forming a dual anti-settling mechanism of steric hindrance and electrostatic stabilization, and can also make the dispersion degree D90 of the inorganic filler ≤ 5μm. In addition, the hydroxyl group of the inorganic filler chemically reacts with the isocyanate group (-NCO) in the resin matrix, which can effectively enhance the interfacial bonding strength between the inorganic filler and the resin matrix, thereby improving the adhesion of the coating.

[0052] (6) This application utilizes phenolic compounds as light stabilizers, which form π-π conjugated protection with the siloxane bonds of the resin matrix through intramolecular hydrogen bonds, further inhibiting UV degradation. Furthermore, the synergistic effects of the resin matrix, light stabilizer, and anti-settling agent can reduce the luminous efficiency decay rate of the coating to ≤8% after one year of outdoor exposure, while maintaining adhesion at level 3B.

[0053] (7) The self-luminous coating material described in this application has the properties of high brightness, long afterglow, strong adhesion, and aging resistance. It has good application prospects in the self-luminous identification systems of the transportation field (such as reflective markings on highways, tunnel emergency guidance signs, airport runway boundary markings, etc.), fire emergency field (such as safety exit indication systems, escape route ground markings, fire facility positioning markings, etc.), architectural landscape field (such as building exterior wall decorative lighting, garden trail night guidance, underwater landscape lighting systems, etc.), industrial facility field (such as chemical plant pipeline markings, oil and gas storage tank safety warnings, mine underground navigation systems, etc.) and other fields. DETAILED DESCRIPTION

[0054] The present invention will be further described below with reference to specific embodiments, wherein the methods are conventional methods unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified.

[0055] Example 1

[0056] A self-luminous coating material, comprising, by weight, 30 parts of modified luminous powder (18 parts of modified luminous powder with a particle size of 8±0.5 μm and 12 parts of modified luminous powder with a particle size of 12±0.5 μm), 18 parts of a resin matrix, 5 parts of an inorganic filler, 0.2 parts of a defoaming agent, 0.2 parts of a leveling agent, 0.5 parts of a thickener, 1.5 parts of a film-forming aid, 0.7 parts of a toughening agent, 0.6 parts of a dispersant, 0.5 parts of a light stabilizer, and 1 part of an anti-settling agent; wherein the modified luminous powder is a rare earth aluminate SrAl2O4:Eu coated with a silica layer. 2+ ,Dy 3+ ,Cu + ,Mn 2+ The resin matrix is ​​PDMS-PU-PMMA block copolymer, and the inorganic filler is selected with a specific surface area of ​​200-300m 2 / g range of hydroxylated nano-scale fumed silica, the defoaming agent is emulsified methyl silicone oil, the leveling agent is polyether modified siloxane, the thickener is polyurethane modified polyether, the film-forming aid is propylene glycol methyl ether acetate, the toughening agent is dibutyl phthalate, the dispersant is silane coupling agent KH-570, the light stabilizer is 2-(2H-benzotriazole-2-yl)-4,6-di-tert-amylphenol, and the anti-settling agent is aluminum stearate.

[0057] The preparation of the self-luminous coating material comprises the following steps:

[0058] (1) Preparation of modified luminous powder

[0059] 1.1) SrCO3 (purity ≥99.9%), Al2O3 (purity ≥99.9%), Eu2O3 (purity ≥99.9%), Dy2O3 (purity ≥99.99%), CuO (purity ≥99.9%), and MnCO3 (purity ≥99.9%) were weighed in a stoichiometric ratio, wherein the matrix material was weighed at a molar ratio of SrCO3:Al2O3 = 1:1, and the dopant was weighed at a total doping amount of ≤5 mol% (the total doping amount was not more than 5 mol per 100 mol). 2+ =1 mol%, Dy 3+ =1mol%Cu + =0.5mol%Mn 2+ =0.15 mol%;

[0060] The weighed raw materials were mixed with anhydrous ethanol at a solid-liquid ratio of 1:2 (the mass ratio of the sum of the mass of all raw materials to anhydrous ethanol was 1:2), and zirconia ball milling beads were added. The mixture was ball milled at 300 rpm for 6 h. After ball milling, the slurry was vacuum dried at 80 ° C for 12 h to obtain a uniform mixed powder;

[0061] The mixed powder was placed in an Al2O3 crucible, heated to 1350℃ at 5℃ / min in a reducing atmosphere of H2 / N2 (volume ratio 5:95) and kept warm for 6h, then cooled and crushed and sieved to obtain SrAl2O4:Eu particles with a particle size of 1-5μm. 2+ ,Dy 3+ ,Cu + ,Mn 2+ powder;

[0062] 1.2) Take SrAl2O4:Eu with a particle size of 1-5μm 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder (purity>99.9%) was first ultrasonically cleaned with anhydrous ethanol for 30 minutes to remove the surface organic matter, and then immersed in a 0.2 mol / L sodium hydroxide solution at 55 ° C for 1.5 hours. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A hydroxylated layer is formed on the surface of the powder;

[0063] 1.3) Tetraethyl orthosilicate (TEOS), anhydrous ethanol, and deionized water were mixed in a volume ratio of 1:4:0.5. A CTAB template was added at a molar concentration of 0.01 mol / L (the concentration of CTAB in the reaction system was 0.01 mol / L) and a KH-570 silane coupling agent was added at a mass fraction of 0.5 wt% (the mass fraction of KH-570 in the reaction system was 0.5%). 0.1 mol / L HCl was then added dropwise to adjust the pH of the reaction system to 3. The mixture was stirred for 2 h to form a transparent sol, thereby obtaining a SiO2 sol.

[0064] SrAl2O4:Eu with a hydroxylated layer on the surface 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder and SiO2 sol are mixed in a mass ratio of 1:20 and uniformly mixed by ultrasonic dispersion for 25 minutes. Then, the mixture is stirred and reacted for 1 hour at pH = 3 and 25 ° C to form an initial SiO2 core layer. Then, an alkaline solution (such as ammonia water) is added dropwise to adjust the pH to 7 and the temperature is adjusted to 60 ° C. The mixture is stirred and reacted for 2 hours to form a SiO2 layer. Then, a silicon source solution (such as 0.1 mol / L Na2SiO3 solution) is added to adjust the pH to 10 and the temperature is adjusted to 80 ° C. The mixture is stirred and aged for 4 hours to densify the surface of the SiO2 layer. Finally, the mixture is centrifuged and washed 3 times with anhydrous ethanol to obtain SrAl2O4:Eu with a surface coated with a 70 nm thick SiO2 layer. 2+ ,Dy 3+ ,Cu+ ,Mn 2+ powder;

[0065] 1.4) SrAl2O4:Eu with SiO2 layer on the surface 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder was dried under vacuum at 55°C for 12 h, then heated to 300±10°C at a rate of 2°C / min and kept warm for 2 h, then placed in an oxygen atmosphere and kept warm at 500±20°C for 2 h, and finally ground and sieved to obtain the modified luminous powder of the desired particle size.

[0066] (2) Preparation of resin matrix

[0067] 2.1) A bifunctional hydroxypropyl silicone oil (PDMS-OH, Mn = 2000 g / mol) and isophorone diisocyanate (IPDI) were mixed in a molar ratio of 1:2.2. A 0.05 wt.% mass fraction of dibutyltin dilaurate (DBTDL) catalyst was added (the mass fraction of DBTDL in the reaction system was 0.05%). The mixture was reacted at 70°C under nitrogen for 3 h to produce a PDMS prepolymer containing isocyanate groups at both ends (PDMS-NCO). The prepolymer was then capped with hydroxyethyl acrylate (HEA) in a molar ratio of PDMS-NCO:HEA = 1:1.2. The mixture was reacted at 60°C for 2 h to obtain an acrylate-terminated silicone block (PDMS-HEA).

[0068] 2.2) 2-Cyano-2-propylbenzotrithiocarbonate (CPBT) and toluene were mixed in a volume ratio of 1:5, and EtAl(ODBP)2 was added as a ligand at a molar concentration of 0.1 mol / L (the molar concentration of EtAl(ODBP)2 in the reaction system was 0.1 mol / L) to form an active RAFT system. Polycaprolactone diol (PCL, Mn = 2000 g / mol) and IPDI were added to the RAFT system at a molar ratio of PCL:IPDI:RAFT system = 1:2:1, and the mixture was reacted at 50°C for 4 h to form a polyurethane prepolymer (PU). A mixture of methyl methacrylate (MMA) and AM-314 in a molar ratio of 9:1 was added dropwise to the PU, and the mixture was heated to 70°C for 6 h. Crosslinking was induced by intermittent irradiation with ultraviolet light (365 nm) to obtain polyurethane-acrylic resin blocks (PU-PMMA).

[0069] 3) PDMS-HEA and PU-PMMA were mixed in a molar ratio of 1:1, and a KH-570 silane coupling agent was added at a mass fraction of 0.5 wt.% (the mass fraction of KH-570 in the reaction system was 0.5%). After ultrasonic dispersion for 30 minutes, a thiol-ene click reaction was performed by UV irradiation for 60 seconds to achieve block covalent bonding. The mixture was then calcined at 300°C for 2 hours to remove residual monomers, and then calcined again at 500°C for 1 hour to strengthen interfacial bonding. Self-assembly was then induced by solvent evaporation, wherein THF / water (volume ratio 7:3) was used as the solvent system to obtain a layered ordered structure of PDMS-PU-PMMA block copolymer, i.e., a resin matrix was obtained;

[0070] (3) Mix the resin matrix and the film-forming aid according to weight, and stir at 500 rpm for 20 minutes to form a uniform emulsion; vacuum dry the modified luminous powder at 80°C for 2 hours to make its moisture content ≤0.1%, then slowly add the dried modified luminous powder, dispersant and defoaming agent into the uniform emulsion, and disperse at 800±50 rpm for 40 minutes to make it uniformly mixed. Note that the system temperature should be controlled at ≤40°C during the high-speed dispersion and mixing process; then add inorganic filler, light stabilizer, anti-settling agent and toughening agent, and disperse at 1200±100 rpm for 1 hour to make the dispersion degree D90 of the inorganic filler ≤5μm; finally, add the leveling agent and thickener, wherein the thickener is added step by step (0.1-0.3 parts each time, with an interval of 5-15 minutes) and the viscosity is monitored in real time (rotational viscometer, 25°C) and dynamically adjusted to 2000-4000 mPa·s, and finally filtered through a 200-mesh sieve to obtain a self-luminous coating material.

[0071] The self-luminous coating material prepared in Example 1 was drop-coated on the sleeve. The 320 μm thick coating formed on the sleeve had an initial luminous intensity of about 1.8 cd / m 2 The luminous time is 16h, the peel strength of the coating is greater than 50N / m, the adhesion grade is 2B, the surface drying is less than 30min, the actual drying is less than 10h, there is no obvious yellowing after being placed outdoors for 2 months, and the luminous efficiency attenuation rate after 1 year of outdoor exposure is about 7%.

[0072] Example 2

[0073] On the basis of Example 1, the film-forming aid substance is replaced with polyvinyl pyrrolidone, and the content of modified luminous powder is changed to 35 parts (20 parts of modified luminous powder with a particle size of 8±0.5μm, and 15 parts of modified luminous powder with a particle size of 12±0.5μm), the resin matrix content is changed to 20 parts, the inorganic filler content is changed to 8 parts, the film-forming aid content is changed to 2 parts, the toughening agent content is changed to 0.6 parts, the dispersant content is changed to 0.8 parts, and the light stabilizer content is changed to 0.6 parts. The types and contents of other components are the same as in Example 1, and the self-luminous coating material is obtained according to the preparation conditions of Example 1.

[0074] The self-luminous coating material prepared in Example 2 was drop-coated on the sleeve. The 350 μm thick coating formed on the sleeve had an initial luminous intensity of about 2.0 cd / m 2 The luminous time is 18h, the peel strength of the coating is greater than 50N / m, the adhesion grade is 2B, the surface drying is less than 30min, the actual drying is less than 10h, there is no obvious yellowing after being placed outdoors for 2 months, and the luminous efficiency attenuation rate after 1 year of outdoor exposure is about 6%.

[0075] Example 3

[0076] On the basis of Example 1, the toughening agent was replaced with triphenyl phosphate, and the content of the modified luminous powder was changed to 45 parts (25 parts of the modified luminous powder with a particle size of 8±0.5 μm, and 20 parts of the modified luminous powder with a particle size of 12±0.5 μm), the resin matrix content was changed to 25 parts, the inorganic filler content was changed to 10 parts, the defoaming agent content was changed to 0.5 parts, the leveling agent content was changed to 0.3 parts, the thickener content was changed to 1 part, the film-forming aid content was changed to 2.5 parts, the toughening agent content was changed to 0.9 parts, the dispersant content was changed to 0.8 parts, the light stabilizer content was changed to 0.8 parts, and the anti-settling agent content was changed to 1.5 parts. The types and contents of other components were the same as those in Example 1, and the self-luminous coating material was obtained according to the preparation conditions of Example 1.

[0077] The self-luminous coating material prepared in Example 3 was drop-coated on the sleeve. The initial luminous intensity of the 400 μm thick coating formed on the sleeve was about 2.0 cd / m 2 The luminous time is 18h, the peel strength of the coating is greater than 50N / m, the adhesion grade is 2B, the surface drying is less than 30min, the actual drying is less than 10h, there is no obvious yellowing after being placed outdoors for 2 months, and the luminous efficiency attenuation rate after 1 year of outdoor exposure is about 6%.

[0078] Example 4

[0079] Based on Example 1, the only difference is that a modified luminous powder with a particle size of 12±0.5 μm is used, and the material types and contents of other components are the same as those in Example 1, and the self-luminous coating material is obtained according to the preparation conditions of Example 1.

[0080] The self-luminous coating material prepared in Example 4 was drop-coated on the sleeve. The initial luminous intensity of the 400 μm thick coating formed on the sleeve was about 1.1 cd / m 2 The luminous time is 10h, the peel strength of the coating is greater than 50N / m, the adhesion grade is 2B, the surface drying is less than 30min, the actual drying is less than 10h, there is no obvious yellowing after being placed outdoors for 2 months, and the luminous efficiency attenuation rate after 1 year of outdoor exposure is about 15%.

[0081] Example 5

[0082] Based on Example 1, the only difference is that the Cu + With Mn 2+ The molar ratio of SrCO3:Al2O3 is 1:1. Accordingly, in step (1.1), the matrix raw material is weighed according to the molar ratio of SrCO3:Al2O3=1:1, and the dopant is weighed according to the total doping amount ≤5mol% (the total doping amount is not more than 5mol per 100mol). 2+ =1 mol%, Dy 3+ =1mol%Cu + =0.5mol%Mn 2+ =0.5 mol %, the types and contents of other components are the same as those in Example 1, and the self-luminous coating material is obtained according to the preparation conditions of Example 1.

[0083] The self-luminous coating material prepared in Example 5 was drop-coated on the sleeve. The 360 ​​μm thick coating formed on the sleeve had an initial luminous intensity of about 1.2 cd / m 2 The luminous time is 11h, the peel strength of the coating is greater than 50N / m, the adhesion grade is 2B, the surface drying is less than 30min, the actual drying is less than 10h, there is no obvious yellowing after being placed outdoors for 2 months, and the luminous efficiency attenuation rate after 1 year of outdoor exposure is about 18%.

[0084] Comparative Example 1

[0085] On the basis of Example 1, the SrAl2O4:Eu modified by silica coating 2+ ,Dy 3+ ,Cu + ,Mn 2+ The luminous powder is replaced with unmodified SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn2+ The types and contents of the luminous powder and other components are the same as those in Example 1, and the self-luminous coating material is obtained according to the preparation conditions of Example 1.

[0086] The self-luminous coating material prepared in Comparative Example 1 was drop-coated on the sleeve. The 450 μm thick coating formed on the sleeve had an initial luminous intensity of about 800 mcd / m 2 , the luminous time is 10h.

[0087] Comparative Example 2

[0088] On the basis of Example 1, the type of resin matrix was changed from PDMS-PU-PMMA block copolymer to polymethyl methacrylate, the types and contents of other components were the same as those in Example 1, and the self-luminous coating material was obtained according to the preparation conditions of Example 1.

[0089] The self-luminous coating material prepared in Comparative Example 2 was drop-coated on the sleeve. The 380 μm thick coating formed on the sleeve had an initial luminous intensity of about 1.1 cd / m 2 The luminous time is 11h. The luminous efficiency decay rate of the coating after one year of outdoor exposure is about 20%, and the adhesion grade is 2B.

[0090] Comparative Example 3

[0091] On the basis of Example 1, except that no light stabilizer was added, the types and contents of other components were the same as those in Example 1, and the self-luminous coating material was obtained according to the preparation conditions of Example 1.

[0092] The self-luminous coating material prepared in Comparative Example 3 was drop-coated on the sleeve. The 320 μm thick coating formed on the sleeve had an initial luminous intensity of about 1.02 cd / m 2 The luminous time is 10h. The luminous efficiency attenuation rate of the coating after 1 year of outdoor exposure is about 18%, and the adhesion grade is 2B.

[0093] Comparative Example 4

[0094] On the basis of Example 1, except that the water content of the modified luminous powder used in step (3) is 0.7%, the types and contents of other components are the same as those in Example 1, and the self-luminous coating material is obtained according to the preparation conditions of Example 1.

[0095] The self-luminous coating material prepared in Comparative Example 4 was drop-coated on the sleeve. The 450 μm thick coating formed on the sleeve had an initial luminous intensity of about 1.1 cd / m 2 The luminous time is 4h. The luminous efficiency attenuation rate of the coating after 1 year of outdoor exposure is about 15%, and the adhesion grade is 2B.

[0096] Comparative Example 5

[0097] On the basis of Example 1, except that no anti-settling agent was added, the types and contents of other components were the same as those in Example 1, and the self-luminous coating material was obtained according to the preparation conditions of Example 1.

[0098] The self-luminous coating material prepared in Comparative Example 5 was drop-coated on the sleeve. The initial luminous intensity of the 300 μm thick coating formed on the sleeve was about 1.3 cd / m 2 The luminous time is 13h. The luminous efficiency attenuation rate of the coating after one year of outdoor exposure is about 14%, and the adhesion grade is 2B.

[0099] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A self-luminous coating material, characterized in that: The self-luminous coating material comprises, by weight: Modified luminous powder, 30-45 parts, is a rare earth aluminate with a surface coated with a silicon dioxide layer. The chemical formula of the rare earth aluminate is SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ ; Resin matrix, 18-25 parts, is a silicone-polyurethane-polymethyl methacrylate triblock copolymer; Inorganic filler, 5-10 parts; Light stabilizer, 0.5-0.8 parts; Anti-settling agent, 1-1.5 parts; Film-forming aid, 1.5-2.5 parts; Defoaming agent, 0.2-0.5 parts; Leveling agent, 0.1-0.3 parts; Thickener, 0.5-1 part; Toughener, 0.6-0.9 parts; Dispersant, 0.6-0.8 parts.

2. A self-luminous coating material according to claim 1, characterized in that: The particle size of the modified luminous powder is 6-14μm; or, The modified luminous powder includes two particle sizes: 8±0.5μm and 12±0.5μm, and the mass ratio of the modified luminous powder with a particle size of 8±0.5μm to the modified luminous powder with a particle size of 12±0.5μm is 55:45-65:35; or / and, Cu in rare earth aluminates + With Mn 2+ The molar ratio is 1:0.3-1:0.5; or / and, The thickness of the silicon dioxide layer coated on the surface of the rare earth aluminate is 50-120 nm.

3. The self-luminous coating material according to claim 1, characterized in that: The inorganic filler comprises at least one of fumed silica, alumina and titanium dioxide; or / and, The light stabilizer is a phenolic compound; or / and, The anti-settling agent includes at least one of aluminum stearate, zinc stearate and polyamide wax; or / and, The film-forming aid includes at least one of propylene glycol methyl ether acetate, polyvinyl pyrrolidone and dipropylene glycol methyl ether; or / and, The defoaming agent is at least one of an organosilicon defoaming agent and a mineral oil defoaming agent; or / and, The leveling agent is selected from at least one of polyether modified silicone and fluorocarbon surfactant; or / and, The thickener is selected from at least one of polyurethane-modified polyether and hydrophobically modified cellulose; or / and, The toughening agent is selected from at least one of dibutyl phthalate and triphenyl phosphate; The dispersant is selected from at least one of a silane coupling agent and a polycarboxylate polymer dispersant.

4. The self-luminous coating material according to claim 1, characterized in that: The inorganic filler is hydroxylated nano-sized fumed silica; or / and, The light stabilizer is 2-(2H-benzotriazole-2-yl)-4,6-di-tert-amylphenol; or / and, The anti-settling agent is aluminum stearate.

5. The self-luminous coating material according to claim 1, characterized in that: The inorganic filler is hydroxylated nano-scale fumed silica, the anti-settling agent is aluminum stearate, and the mass ratio of the hydroxylated nano-scale fumed silica to the aluminum stearate is 1:0.1-1:0.

3.

6. A method for preparing a self-luminous coating material according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is immersed in an alkaline solution to form a hydroxylated layer on its surface; SrAl2O4:Eu with a hydroxylated layer on the surface 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is dispersed in SiO2 sol, and the pH is adjusted in the range of 2.5-10.

5. The reaction is carried out at 20-85℃. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A silicon dioxide layer of desired thickness is formed on the surface of the powder; SrAl2O4:Eu coated with a silicon dioxide layer 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is first dried and then calcined at 290-520°C for 3-5 hours to obtain the modified luminous powder; (2) The resin matrix and the film-forming aid are mixed evenly to form a uniform emulsion; the dried modified luminous powder, dispersant, and defoaming agent are added to the uniform emulsion, stirred and mixed evenly, and then the inorganic filler, light stabilizer, anti-settling agent, and toughening agent are added, and the stirring and mixing are continued. Finally, the leveling agent and thickener are added, and the stirring and mixing are continued to obtain a self-luminous coating material.

7. The method for preparing a self-luminous coating material according to claim 6, characterized in that: Unmodified luminous powder SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The preparation method is as follows: SrCO3, Al2O3, Eu2O3, Dy2O3, CuO and MnCO3 are weighed according to the stoichiometric ratio, the weighed raw materials are added to a ball mill for wet ball milling dispersion, and the ball-milled slurry is vacuum dried to obtain a uniformly mixed powder; the mixed powder is placed in a reducing atmosphere, calcined at 1300-1400 ° C for 6-7 hours, and then cooled and crushed and sieved to obtain SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ powder; or, In SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The formation of the hydroxylation layer on the powder surface includes the following specific steps: SrAl2O4:Eu 2+ ,Dy 3+ ,Cu + ,Mn 2+ The powder is immersed in an alkali metal hydroxide solution with a concentration of 0.05-0.5 mol / L and immersed at 50-70 ° C for 1-3 hours. 2+ ,Dy 3+ ,Cu + ,Mn 2+ A hydroxylated layer is formed on the surface of the powder; or, SrAl2O4:Eu with a hydroxylated layer on the surface 2+ ,Dy 3+ ,Cu + ,Mn 2+ The formation of SiO2 layer on the powder surface includes the following specific steps: 2+ ,Dy 3+ ,Cu + ,Mn 2+ After the powder and SiO2 sol are evenly mixed in a mass ratio of 1:10-1:30, the mixture is first reacted at 20-35°C for 0.5-1.5h in the range of pH = 2.5-3.5 to form an initial SiO2 core layer, and then the pH is adjusted to 6.5-7.5, and the mixture is continued to react at 55-65°C for 1.5-3h to form a SiO2 layer, and then the pH is adjusted to 9.5-10.5, and the mixture is aged at 75-85°C for 3-5h to densify the surface of the SiO2 layer. 2+ ,Dy 3 + ,Cu + ,Mn 2+ A SiO2 layer of desired thickness is formed on the surface of the powder.

8. The method for preparing a self-luminous coating material according to claim 6, characterized in that: The resin matrix was prepared by the following method: (1) Bis-terminal hydroxypropyl silicone oil and isophorone diisocyanate are mixed in a molar ratio of 1:2.0-1:2.5, and a catalyst is added at a mass fraction of 0.05-0.08%, and the mixture is reacted at 65-75°C for 2-4 hours under N2 or inert gas protection to generate a PDMS prepolymer containing isocyanate groups at both ends, abbreviated as PDMS-NCO; hydroxyethyl acrylate is then added at a molar ratio of PDMS-NCO:hydroxyethyl acrylate = 1:(1.0-1.4) to block the ends, and the mixture is reacted at 55-65°C for 2-3 hours to obtain an acrylate-terminated silicone block, abbreviated as PDMS-HEA; (2) 2-cyano-2-propylbenzotrithiocarbonate and toluene are mixed in a volume ratio of 1:4-1:6, and bis(1,1′-(1,3,4-oxadiazole-2,5-diyldi-4,1-phenylene)-4-butoxy-2-methylbenzoate)ethylaluminum is added as a ligand and its concentration after addition is 0.05-0.2 mol / L to form an active RAFT system; the molar ratio of polycaprolactone diol:isophorone diisocyanate:RAFT system is 1:( 1.8-2.2):

1. Add polycaprolactone diol and isophorone diisocyanate to a RAFT system, and react at 50-60° C. for 4-5 hours to generate a polyurethane prepolymer; add a mixture of methyl methacrylate and 2-ethylhexyl acrylate in a molar ratio of 8:1-10:1 to the polyurethane prepolymer, heat to 70-80° C., react for 6-7 hours, and induce crosslinking by intermittent ultraviolet light irradiation to obtain a polyurethane-acrylic resin block, abbreviated as PU-PMMA; (3) PDMS-HEA and PU-PMMA were mixed in a molar ratio of 1:0.9-1:1.1, and a silane coupling agent was added at a mass fraction of 0.5%. After ultrasonic dispersion, a thiol-ene click reaction was performed by UV irradiation to achieve block covalent connection. After annealing treatment and solvent evaporation, self-assembly was induced to form a layered ordered PDMS-PU-PMMA triblock structure.

9. The method for preparing a self-luminous coating material according to claim 6, characterized in that: The moisture content of the dried modified luminous powder is not more than 0.1wt.%; or / and, After adding the dispersant, stirring and mixing were performed at a temperature below 45°C.

10. A use of a self-luminous coating material according to any one of claims 1 to 5, characterized in that: The self-luminous coating material is used to prepare self-luminous signs in the fields of transportation, fire emergency, architectural landscape, and industrial facilities.