Self-luminous epoxy resin composite coating and preparation method thereof

Abstract

The invention discloses a self-luminous epoxy resin composite coating and a preparation method thereof. The coating comprises the following raw materials in parts by weight: 20-30 parts of a curing agent, 0.1-0.2 parts of a defoaming agent, 0.5-2 parts of a thickener, 1-3 parts of a plasticizer, 1-3 parts of water, 10-15 parts of a water-based epoxy resin, 20-40 parts of a long-lasting glow phosphor, 2-10 parts of a modifier, and 1-5 parts of a coupling agent. The modifier is at least one of amino polyhedral oligomeric silsesquioxane, chlorine-based polyhedral oligomeric silsesquioxane, and vinyl polyhedral oligomeric silsesquioxane. The coating modifies the long-lasting glow phosphor with the polyhedral oligomeric silsesquioxane, significantly improving the friction resistance and water resistance of the coating while significantly improving the luminous efficiency and brightness of the long-lasting glow phosphor in the water-based epoxy resin. The obtained composite coating has better optical properties, which is conducive to the large-scale promotion and application of the self-luminous epoxy resin composite coating.

Description

Technical Field

[0001] The present invention relates to the field of coatings, in particular to the field of self-luminous coatings, and specifically to a self-luminous epoxy resin composite coating and a preparation method thereof. Background Art

[0002] Epoxy resin coatings have excellent alkali resistance and adhesion, and as the resin matrix for self-luminous coatings, they have great application prospects. However, traditional organic solvent-based epoxy resins are subject to environmental pollution issues and do not meet environmental and green requirements, limiting their large-scale application in the coatings field. Water-based epoxy resins, as an environmentally friendly resin matrix, are non-toxic, odorless, and free of organic solvents, which can well meet environmental protection requirements and have great application prospects in the coatings field.

[0003] Long-lasting inorganic materials have the advantages of high luminous efficiency, long afterglow time, and are non-toxic and non-radioactive. They are excellent green and environmentally friendly self-luminous materials. Therefore, the combination of long-lasting materials and water-based epoxy resins to prepare self-luminous coatings has great application potential. However, long-lasting materials are easily hydrolyzed by moisture in aqueous environments, resulting in a significant reduction in their luminous intensity and afterglow time. At the same time, as inorganic powder materials, long-lasting luminous materials have poor compatibility with organic resin matrices, and there are agglomeration and stratification phenomena during the preparation process, which leads to the defects of poor friction resistance, poor adhesion, and poor weather resistance in self-luminous coatings. Due to the above problems, the application of self-luminous water-based epoxy resin coatings is greatly limited. Therefore, they must be modified to improve the above problems of self-luminous water-based epoxy resin coatings.

[0004] Currently, the commonly used methods for improving the compatibility between inorganic and organic materials are mainly physical coating and chemical grafting modification. However, during the experiment, it was found that both methods have certain shortcomings when improving the compatibility between long-lasting inorganic materials and water-based epoxy resin matrices: chemical grafting modification has a low grafting rate with the long-lasting inorganic materials, resulting in poor modification effect; while physical coating modification, although it has a good improvement in the water resistance of the long-lasting inorganic materials, is not conducive to the compatibility between the long-lasting inorganic materials and the water-based epoxy resin matrix. Moreover, because the dispersibility and water resistance of the long-lasting materials cannot be well improved at the same time, the optical properties of the modified self-luminous water-based epoxy resin coating are significantly reduced, which is obviously not conducive to the large-scale promotion and application of self-luminous water-based epoxy resin coatings. Summary of the Invention

[0005] The purpose of the present invention is to provide a self-luminous epoxy resin composite coating and a preparation method thereof in response to the problems of poor water resistance, optical properties and friction resistance of existing self-luminous water-based epoxy resin coatings. The self-luminous epoxy resin composite coating is modified by polyhedral oligomeric silsesquioxane on a long-lasting phosphor, which significantly improves the friction resistance and water resistance of the composite coating while significantly reducing the influence of the water-based epoxy resin on the luminous efficiency and brightness of the long-lasting phosphor, so that the obtained composite coating has better optical properties, which is conducive to the large-scale promotion and application of the self-luminous epoxy resin composite coating.

[0006] In order to achieve the above-mentioned object, the present invention provides a self-luminous epoxy resin composite coating, which is prepared by including the following raw materials in parts by weight: 20-30 parts of a curing agent, 0.1-0.2 parts of a defoaming agent, 0.5-2 parts of a thickener, 1-3 parts of a plasticizer, 1-3 parts of water, 10-15 parts of a water-based epoxy resin, 20-40 parts of a long-lasting phosphor, 2-10 parts of a modifier and 1-5 parts of a coupling agent; wherein the modifier is at least one of amino polyhedral oligomeric silsesquioxane, chlorine-based polyhedral oligomeric silsesquioxane and vinyl polyhedral oligomeric silsesquioxane.

[0007] The present invention discloses a self-luminous epoxy resin composite coating, which modifies long-lasting phosphor by using polyhedral oligomeric silsesquioxane. The polyhedral oligomeric silsesquioxane is used to coat the long-lasting phosphor, thereby significantly improving the water resistance of the long-lasting phosphor and its compatibility with water-based epoxy resin, so that the obtained composite coating has excellent friction resistance and water resistance. At the same time, since the dispersibility and water resistance of the long-lasting phosphor are improved, the luminous efficiency and brightness of the modified self-luminous epoxy resin composite coating are significantly improved. In addition, the nano-properties of the polyhedral oligomeric silsesquioxane are utilized to make the coating layer formed by the polyhedral oligomeric silsesquioxane have excellent light transmittance, thereby further significantly reducing the influence of the coating layer and the water-based epoxy resin on the luminous efficiency and brightness of the long-lasting phosphor, so that the obtained composite coating has better optical properties, which is conducive to the large-scale promotion and application of the self-luminous epoxy resin composite coating.

[0008] Among them, preferably, the modifier is a chlorine-based polyhedral oligomeric silsesquioxane; with the preferred type of modifier, the self-luminous coating obtained has better water resistance and optical properties.

[0009] Among them, preferably, the (average) degree of polymerization of the modifier is 10-50; the preferred degree of polymerization of the modifier, the formed coating has better optical properties, and the obtained composite coating has better optical properties; more preferably, the degree of polymerization of the modifier is 20-30.

[0010] Among them, preferably, the curing agent is 650 polyamide curing agent; the preferred curing agent has a fast curing speed, better performance of the coating after curing, and less pollution to the environment.

[0011] Among them, preferably, the defoaming agent is a polysiloxane defoaming agent; the preferred defoaming agent has good defoaming effect and the obtained coating has better performance.

[0012] Among them, preferably, the thickener is polyether polyurethane; the preferred thickener has good thickening effect, better adhesion, and is more conducive to the use of the coating.

[0013] Among them, preferably, the plasticizer is ethylene glycol monobutyl ether; the preferred plasticizer has better leveling properties of the coating, which is beneficial to the uniformity of the coating when brushed.

[0014] Among them, preferably, the water-based epoxy resin is E44 type epoxy resin; the preferred type of water-based epoxy resin has better comprehensive performance and the resulting coating has better luminous performance.

[0015] Among them, preferably, the long-lasting phosphor is a silicate-based long-lasting phosphor; the luminescence performance of the preferred long-lasting phosphor type is less affected by coupling agents and modifiers, and the resulting composite coating has better luminescence performance.

[0016] Among them, preferably, the coupling agent is at least one of γ-aminopropyltriethoxysilane, (3-epoxyethylmethoxypropyl)trimethoxysilane and (3-mercaptopropyl)triethoxysilane; the preferred type of coupling agent can better couple the long-lasting glow phosphor, which is beneficial to improving the modification effect of the long-lasting glow phosphor.

[0017] To achieve the above-mentioned object of the invention, the present invention further provides a method for preparing a self-luminous epoxy resin composite coating, comprising the following steps:

[0018] (1) performing coupling treatment on the long-lasting phosphor using a coupling agent to obtain a long-lasting phosphor treated with the coupling agent;

[0019] (2) After the modifier is dispersed and dissolved in an organic solvent, the long-lasting phosphor treated with a coupling agent is added, and the mixture is stirred at 80-100° C. for 4-8 hours. The modified long-lasting phosphor is obtained by filtering, washing, and drying.

[0020] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0021] Among them, preferably, in step (1), the coupling treatment includes: dispersing and dissolving the coupling agent with ethanol, adding the long-lasting phosphor, stirring and reacting at 30-50° C. for 1-3 hours, and filtering, washing and drying to obtain the long-lasting phosphor treated with the coupling agent.

[0022] Preferably, the mass fraction of the coupling agent in ethanol is 1-5%; ethanol is used for washing; and the drying temperature is not higher than 100° C. The preferred coupling treatment conditions have a better coupling treatment effect on the long-lasting phosphor and are beneficial to improving the modification effect of the long-lasting phosphor.

[0023] Wherein, preferably, in step (2), the organic solvent is N,N-dimethylformamide (DMF).

[0024] Preferably, the mass fraction of the modifier in the organic solvent is 1-5%; ethanol is used for washing; and drying is carried out in a vacuum or inert atmosphere at a temperature of 70-90° C. for 10-14 hours. The preferred modification conditions have a better modification effect on the long-lasting phosphor.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The self-luminous epoxy resin composite coating of the present invention utilizes polyhedral oligomeric silsesquioxane to coat the long-lasting phosphor, thereby significantly improving the water resistance of the long-lasting phosphor and its compatibility with water-based epoxy resin, so that the obtained composite coating has excellent friction resistance and water resistance.

[0027] 2. The self-luminous epoxy resin composite coating of the present invention utilizes the nano-properties of polyhedral oligomeric silsesquioxane to make the coating layer formed by the polyhedral oligomeric silsesquioxane have excellent light transmittance, thereby significantly reducing the influence of the coating layer and water-based epoxy resin on the luminous efficiency and brightness of the long-lasting phosphor, so that the obtained composite coating has better optical properties.

[0028] 3. The preparation method of the self-luminous epoxy resin composite coating of the present invention is simple, reliable, and practical, which is conducive to the large-scale production and application of the self-luminous epoxy resin composite coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 FT-IR spectra of the corresponding long afterglow phosphors in Example 1 and Comparative Example 1 of the present invention;

[0030] Figure 2 These are the EDS images of the corresponding long-lasting phosphors in Example 1 and Comparative Example 1 of the present invention (a is Comparative Example 1; b is Example 1);

[0031] Figure 3Graphs showing the emission spectra of the composite coatings prepared in Example 1 and Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0032] The present invention will be described in further detail below in conjunction with specific embodiments. However, this should not be construed as limiting the scope of the present invention to the following embodiments, as all technologies implemented based on the present invention fall within the scope of the present invention.

[0033] Example 1:

[0034] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long-lasting glow phosphor (brand 207101A), 5 parts of a modifier (amino polyhedral oligomeric silsesquioxane with a degree of polymerization of 30), and 3 parts of a coupling agent ((3-glycidoxy)propyltrimethoxysilane);

[0035] The specific preparation method comprises the following steps:

[0036] (1) After dispersing and dissolving the coupling agent (3 wt %) in ethanol, the long-lasting phosphor was added, stirred and reacted at 40° C. for 2 h, and the long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying;

[0037] (2) After dispersing and dissolving the modifier (3 wt %) in an organic solvent (DMF), the long-lasting phosphor treated with the coupling agent was added, and the mixture was stirred at 90° C. for 6 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80° C., time: 12 h);

[0038] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0039] Example 2:

[0040] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 20 parts of a curing agent (650 polyamide curing agent), 0.2 parts of a defoaming agent (polysiloxane defoaming agent), 0.5 parts of a thickener (polyether polyurethane), 3 parts of a plasticizer (ethylene glycol monobutyl ether), 3 parts of water, 10 parts of an E44 waterborne epoxy resin, 20 parts of a silicate-based long-lasting phosphor (brand 207101A), 2 parts of a modifier (chlorine-based polyhedral oligomeric silsesquioxane with a degree of polymerization of 10), and 1 part of a coupling agent (γ-aminopropyltriethoxysilane).

[0041] The specific preparation method comprises the following steps:

[0042] (1) After dispersing and dissolving the coupling agent (1 wt%) in ethanol, the long-lasting phosphor was added, stirred and reacted at 50° C. for 1 h, and the long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying;

[0043] (2) After dispersing and dissolving the modifier (5 wt %) in an organic solvent (DMF), the long-lasting phosphor treated with the coupling agent was added, and the mixture was stirred at 100° C. for 4 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80° C., time: 10 h);

[0044] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0045] Example 3:

[0046] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 30 parts of a curing agent (650 polyamide curing agent), 0.2 parts of a defoaming agent (polysiloxane defoaming agent), 2 parts of a thickener (polyether polyurethane), 1 part of a plasticizer (ethylene glycol monobutyl ether), 1 part of water, 15 parts of an E44 waterborne epoxy resin, 40 parts of a silicate-based long-lasting glow phosphor, 10 parts of a modifier (vinyl polyhedral oligomeric silsesquioxane with a degree of polymerization of 50), and 5 parts of a coupling agent (3-mercaptopropyltriethoxysilane).

[0047] The specific preparation method comprises the following steps:

[0048] (1) After dispersing and dissolving the coupling agent (5 wt %) in ethanol, the long-lasting phosphor was added, and the mixture was stirred at 30° C. for 3 h. The long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying.

[0049] (2) Weigh 2 wt% of the photocuring agent and dissolve it in a tetrahydrofuran-methanol mixed solution (volume ratio = tetrahydrofuran:methanol = 3:1). Add vinyl POSS (degree of polymerization 20) in a mass ratio of 1:5 to the modified long afterglow powder to the mixed solution, stir to fully dissolve it, then pour the long afterglow luminescent powder modified with the silane coupling agent into it, irradiate it at a distance of 20 cm from the ultraviolet light source for 120 minutes, then air-dry it in a fume hood, wash it once with tetrahydrofuran and then wash it several times with ethanol, and dry it in a vacuum oven at 80°C for 10 hours to obtain the vinyl POSS modified long afterglow powder.

[0050] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0051] Example 4:

[0052] A self-luminous epoxy resin composite coating adopts the raw material composition and preparation method in Example 1, with the only difference being that the polymerization degree of the modifier is different; the polymerization degree of the modifier is shown in Table 1:

[0053] Table 1 Degree of polymerization of modifiers

[0054]

[0055]

[0056] Comparative Example 1:

[0057] A self-luminous epoxy resin composite (long-lasting glow powder / epoxy resin) coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 water-based epoxy resin, and 30 parts of a silicate-based long-lasting glow phosphor (brand 207101A);

[0058] The preparation method thereof comprises the following steps:

[0059] Add curing agent, plasticizer, defoamer, thickener, deionized water and pure long afterglow powder into a beaker, stir and mix evenly, then add water-based epoxy resin to obtain a self-luminous epoxy resin composite coating.

[0060] Comparative Example 2:

[0061] A self-luminous epoxy resin composite (coupling agent modified long afterglow powder / epoxy resin) coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long afterglow phosphor (brand 207101A), and 3 parts of a coupling agent (γ-aminopropyltriethoxysilane);

[0062] The preparation method thereof comprises the following steps:

[0063] (1) Add γ-aminopropyltriethoxysilane to the ethanol solution and stir evenly. Then add the long afterglow powder and stir at 40°C for 2 hours. After sufficient reaction, wash with ethanol several times and dry.

[0064] (2) Add curing agent, plasticizer, defoamer, thickener, deionized water and γ-aminopropyltriethoxysilane modified long afterglow powder into a beaker, stir and mix evenly, then add water-based epoxy resin to obtain a self-luminous epoxy resin composite coating.

[0065] Comparative Example 3:

[0066] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long-lasting phosphor (brand 207101A), and 5 parts of a modifier (amino polyhedral oligomeric silsesquioxane with a degree of polymerization of 20);

[0067] The specific preparation method comprises the following steps:

[0068] (1) After dispersing and dissolving the modifier (3 wt %) in an organic solvent (DMF), the long-lasting phosphor was added and stirred at 90°C for 6 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80°C, time: 12 h);

[0069] (2) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0070] Comparative Example 4:

[0071] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long-lasting glow phosphor (brand 207101A), 12 parts of a modifier (amino polyhedral oligomeric silsesquioxane with a degree of polymerization of 20), and 3 parts of a coupling agent ((3-glycidoxy)propyltrimethoxysilane);

[0072] The specific preparation method comprises the following steps:

[0073] (1) After dispersing and dissolving the coupling agent (3 wt %) in ethanol, the long-lasting phosphor was added, stirred and reacted at 40° C. for 2 h, and the long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying;

[0074] (2) After dispersing and dissolving the modifier (3 wt %) in an organic solvent (DMF), the long-lasting phosphor treated with the coupling agent was added, and the mixture was stirred at 90° C. for 6 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80° C., time: 12 h);

[0075] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0076] Comparative Example 5:

[0077] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long-lasting phosphor (brand 207101A), 5 parts of a modifier (polysiloxane with a degree of polymerization of 20), and 3 parts of a coupling agent (γ-aminopropyltriethoxysilane).

[0078] The specific preparation method comprises the following steps:

[0079] (1) After dispersing and dissolving the coupling agent (3 wt %) in ethanol, the long-lasting phosphor was added, stirred and reacted at 40° C. for 2 h, and the long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying;

[0080] (2) After dispersing and dissolving the modifier (3 wt %) in xylene, the long-lasting phosphor treated with the coupling agent was added, and the mixture was stirred at 90° C. for 6 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80° C., time: 12 h);

[0081] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0082] Comparative Example 6:

[0083] A self-luminous epoxy resin composite coating is prepared by including the following raw materials in parts by weight: 25 parts of a curing agent (650 polyamide curing agent), 0.15 parts of a defoaming agent (polysiloxane defoaming agent), 1.5 parts of a thickener (polyether polyurethane), 2 parts of a plasticizer (ethylene glycol monobutyl ether), 2 parts of water, 13 parts of an E44 waterborne epoxy resin, 30 parts of a silicate-based long-lasting phosphor (brand 207101A), 5 parts of a modifier (ethylene-vinyl acetate copolymer with a degree of polymerization of 20), and 3 parts of a coupling agent (γ-aminopropyltriethoxysilane).

[0084] The specific preparation method comprises the following steps:

[0085] (1) After dispersing and dissolving the coupling agent (3 wt %) in ethanol, the long-lasting phosphor was added, stirred and reacted at 40° C. for 2 h, and the long-lasting phosphor treated with the coupling agent was obtained by filtering, washing, and drying;

[0086] (2) After dispersing and dissolving the modifier (3 wt %) in an organic solvent (DMF), the long-lasting phosphor treated with the coupling agent was added, and the mixture was stirred at 90° C. for 6 h. The modified long-lasting phosphor was obtained by filtration, washing, and drying (temperature: 80° C., time: 12 h);

[0087] (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

[0088] Experimental Example 1:

[0089] The modified long afterglow powder in Example 1 and the unmodified long afterglow powder in Comparative Example 1 and the corresponding self-luminous epoxy resin composite coating were subjected to infrared spectroscopy analysis (FT-IR), X-ray energy spectrum analysis (EDS) and emission spectrum experiments. The results are as follows: Figure 1 、 2 、3.

[0090] analyze Figure 1-3It can be seen that the modification treatment with the modifier in Example 1 of the present invention significantly improves the performance of the long afterglow powder and the composite coating.

[0091] Experimental Example 2:

[0092] The modified long afterglow powders in Examples 1-8 and Comparative Examples 1-7 were subjected to contact angle tests (the contact angle tests of the different modified long afterglow powders were performed using an optical contact angle tester to analyze the samples) and water resistance tests (the samples were placed in an equal amount of deionized water, and the pH of the aqueous phase was measured with a pH meter after 2 hours to compare the effects of different modification methods on the water resistance of the samples); the results are shown in Table 2.

[0093] Table 2

[0094]

[0095]

[0096] Analysis of the experimental results in Table 2 shows that, compared with pure long afterglow powder, the hydrophobicity of the afterglow powder is improved by coating a layer of organic matter on the surface of the long afterglow powder, but the water resistance of the long afterglow powder coated with different materials is different. After the introduction of POSS or other coating materials, the more perfect organic coating reduces the occurrence of hydrolysis reaction and effectively improves the water resistance of the long afterglow powder. At the same time, analysis of the experimental results of Examples 4-8 shows that the degree of polymerization of POSS has a certain influence on the effect of improving the water resistance of the long afterglow powder. The greater the degree of polymerization, the better the water resistance of the modified long afterglow powder.

[0097] Experimental Example 2:

[0098] The brightness of the modified long afterglow powder in Examples 1-8 and Comparative Examples 1-7 was measured (GB / T 24981.2-2020; 6000K light source, illumination 1000lx, temperature 25°C, relative humidity 60%, time 10 min); the composite coatings in Examples 1-8 and Comparative Examples 1-7 were subjected to friction resistance tests (the coating was subjected to a reciprocating friction and wear test on a UMT-2 friction tester (ball disc), GCr15 steel ball as a grinding pair (diameter 6.35 mm), room temperature dry friction, load 8N, stroke 5mm, speed 9mm / s, time 30min) and luminous brightness and afterglow time were measured (T / QGCML 105-2021, 6000K light source, illumination 1000lx, temperature 25°C, relative humidity 60%, time 10min). The results are shown in Table 3.

[0099] Table 3

[0100]

[0101]

[0102] From the analysis of the results in Table 3, it can be seen that compared with the long afterglow powder and composite coating modified with other modifying materials, the long afterglow powder obtained in Examples 1-8 has less effect on the brightness of the afterglow powder after being modified with POSS, and the obtained composite coating has excellent optical properties and is more suitable for large-scale promotion and application.

Claims

1. A self-luminous epoxy resin composite coating, characterized in that: The invention is prepared by comprising the following raw materials in parts by weight: 20-30 parts of a curing agent, 0.1-0.2 parts of a defoaming agent, 0.5-2 parts of a thickener, 1-3 parts of a plasticizer, 1-3 parts of water, 10-15 parts of a water-based epoxy resin, 20-40 parts of a long-lasting phosphor, 2-10 parts of a modifier and 1-5 parts of a coupling agent; wherein the modifier is at least one of amino polyhedral oligomeric silsesquioxane, chlorine-based polyhedral oligomeric silsesquioxane and vinyl polyhedral oligomeric silsesquioxane; and the coupling agent is at least one of γ-aminopropyltriethoxysilane, (3-oxiranylmethoxypropyl)trimethoxysilane and (3-mercaptopropyl)triethoxysilane. In the preparation process of the self-luminous epoxy resin composite coating, a coupling agent is first used to couple the long-lasting phosphor, and then a modifier is used to coat and modify the coupled long-lasting phosphor.

2. The self-luminous epoxy resin composite coating according to claim 1, characterized in that: The degree of polymerization of the modifier is 10-50.

3. The self-luminous epoxy resin composite coating according to claim 1, characterized in that: The defoaming agent is a polysiloxane defoaming agent; the thickener is a polyether polyurethane; and the plasticizer is ethylene glycol monobutyl ether.

4. The self-luminous epoxy resin composite coating according to claim 1, characterized in that: The curing agent is 650 polyamide curing agent.

5. The self-luminous epoxy resin composite coating according to claim 1, characterized in that: The water-based epoxy resin is E44 epoxy resin.

6. The self-luminous epoxy resin composite coating according to claim 1, characterized in that: The long-lasting phosphor is a silicate-based long-lasting phosphor.

7. A method for preparing the self-luminous epoxy resin composite coating according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) Using a coupling agent to couple the long-lasting phosphor to obtain a long-lasting phosphor treated with a coupling agent; (2) After the modifier is dispersed and dissolved in an organic solvent, the long-lasting phosphor treated with a coupling agent is added, and the mixture is stirred at 80-100°C for 4-8 hours. The modified long-lasting phosphor is obtained by filtering, washing and drying. (3) After uniformly mixing the curing agent, plasticizer, defoaming agent, thickener, deionized water and modified long afterglow phosphor, water-based epoxy resin is added to obtain a self-luminous epoxy resin composite coating.

8. The method for preparing the self-luminous epoxy resin composite coating according to claim 7, wherein: In step (1), the coupling treatment comprises: dispersing and dissolving the coupling agent in ethanol, adding the long-lasting phosphor, stirring and reacting at 30-50° C. for 1-3 h, and filtering, washing and drying to obtain the long-lasting phosphor treated with the coupling agent.

9. The method for preparing the self-luminous epoxy resin composite coating according to claim 7, characterized in that: In step (2), the organic solvent is N,N-dimethylformamide.

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