Long-afterglow luminescent road marking paint suitable for road engineering and preparation method thereof

Abstract

The invention discloses a long-afterglow luminous road marking coating suitable for road engineering and a preparation method of the long-afterglow luminous road marking coating, and belongs to the technical field of road engineering. Comprising the following raw materials: 20-30% of a luminescent material, 4-8% of glass powder, 2-6% of titanium dioxide, 0.6% of an anti-settling agent, 2.4% of a coalescing agent, 0.8% of a defoaming agent, 0.8% of a flatting agent and the balance of silicone acrylic emulsion. According to the method, the optimal proportion of the long-afterglow luminescent coating is selected by adopting an orthogonal test-Topsis method, so that the accuracy and scientificity of proportion selection of the long-afterglow luminescent coating are improved, and the road performance verification is performed on the optimal proportion. The long-afterglow luminescent road marking coating has good luminescent performance and road performance, can be used for guiding sight of road marking at night and guaranteeing driving safety, has the advantages of simple preparation method and easiness in control, and is beneficial to popularization and application.

Description

Technical Field

[0001] The invention belongs to the technical field of road engineering, and in particular relates to a long afterglow luminous road marking paint suitable for road engineering and a preparation method thereof. Background Art

[0002] With the rapid development of the transportation industry, my country's highway construction industry has made great progress. However, the imperfect lighting facilities and insufficient night visibility have brought great safety hazards to people's night travel. The accident rate at night is three times that of daytime. At present, the most commonly used solution is to install solar street lights to achieve lighting functions. Although this method can solve the lighting problem well, its cost is high and the installation will consume a lot of manpower and resources.

[0003] The luminous markings painted on the road surface can play a role in guidance and warning, providing longer-distance road line guidance at night to ensure nighttime driving safety. At the same time, it reduces the demand for lighting facilities and reduces energy consumption, which is in line with the concepts of safety, energy saving, and environmental protection in the current environment. Road markings will be damaged to varying degrees as the use time increases and the traffic volume increases, and illegal overloading of vehicles and illegal lane changes of vehicles also cause a certain degree of damage to the markings. At present, conventional long afterglow luminous road marking paints can no longer meet the use requirements of road markings. Therefore, without affecting the luminous performance, it is necessary to develop a long afterglow luminous road marking paint suitable for road engineering. Summary of the invention

[0004] The present invention proposes a long afterglow luminous road marking paint suitable for road engineering and a preparation method thereof, so as to solve the problems of short luminous time, low luminous intensity and poor road performance of the existing long afterglow luminous road marking paint, and at the same time effectively solve the problem that strontium aluminate long afterglow luminous powder has poor water resistance and will undergo hydrolysis reaction when in contact with water or in a humid environment, resulting in a decrease in luminous intensity.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] One of the technical solutions of the present invention:

[0007] A long afterglow luminous road marking paint suitable for road engineering comprises the following raw materials in terms of mass percentage: 20-30% of luminous material, 4-8% of glass powder, 2-6% of titanium dioxide, 0.6% of anti-settling agent, 2.4% of film-forming aid, 0.8% of defoaming agent, 0.8% of leveling agent, and the balance is silicone acrylic emulsion (the sum of the mass percentages of the raw materials is 100%).

[0008] More preferably, the long afterglow luminous road marking paint suitable for road engineering comprises the following raw materials, calculated by mass percentage: 25% luminescent material, 8% glass powder, 2% titanium dioxide, 0.6% anti-settling agent, 2.4% film-forming aid, 0.8% defoaming agent, 0.8% leveling agent, and the remainder is silicone acrylic emulsion (i.e., the mass percentage of silicone acrylic emulsion is 60.4%).

[0009] Preferably, the luminescent material is strontium aluminate long afterglow luminescent powder, and the fineness of the strontium aluminate long afterglow luminescent powder is 100-400 meshes.

[0010] More preferably, the strontium aluminate long afterglow luminescent powder is SrAl2O4:Eu 2+ ,Dy 3+ .

[0011] Preferably, the glass powder has a fineness of 1000-2000 mesh.

[0012] Preferably, the viscosity of the silicone-acrylic emulsion is 200-800 mPa·s. The above viscosity is moderate. If the viscosity of the silicone-acrylic emulsion is too high, the raw materials will be unevenly dispersed in the silicone-acrylic emulsion, thereby affecting the uniformity and water resistance of the luminescent material.

[0013] Preferably, the titanium dioxide is rutile titanium dioxide. The chemical properties of rutile titanium dioxide are stable. Rutile titanium dioxide has a high refractive index, that is, it has good reflectivity in the visible light range. At the same time, rutile titanium dioxide also has good reflectivity in the near-infrared band and is a high-reflectivity pigment filler. In addition, adding rutile titanium dioxide can also achieve a brightening and beautifying effect.

[0014] Preferably, the anti-settling agent is fumed silica, the film-forming aid is alcohol ester twelve, the defoamer is an organosilicon defoamer, and the leveling agent is an aqueous leveling agent. As an anti-settling agent, fumed silica has the functions of thickening and dispersing while preventing precipitation. The film-forming aid is used to reduce the glass transition temperature (Tg) of the resin and promote the extrusion fusion of polymer particles into film. It determines the minimum film-forming temperature and anti-corrosion performance of the coating, and has little effect on the luminous performance of the coating. During the preparation of the coating, stirring will change the surface free energy of the coating system and generate foam. Defoamers are used to destroy the surface viscosity and elasticity of the foaming system, so that the surface tension is unbalanced and the foam is eliminated. The leveling agent can prompt the coating to form a flat, smooth and uniform coating during the drying and film-forming process, so that the surface tension of the coating is in a balanced state, and the uniformity and leveling of the coating are improved.

[0015] Long afterglow material is a new type of environmentally friendly material that can better convert and utilize solar energy. Long afterglow luminescent materials absorb the energy of external light during the day and slowly release the stored energy in the form of visible light at night. They can still emit light for a long time after the light source disappears. They have the advantages of long afterglow time, long service life, energy saving and environmental protection. If long afterglow luminescent materials are combined with road materials and basic supporting facilities, they can provide night lighting for travelers. Although strontium aluminate long afterglow luminescent powder can be added to the coating to make the coating have certain luminescent properties, it has poor compatibility with the raw materials, cannot be evenly dispersed, has poor water resistance, and will undergo hydrolysis when in contact with water or in a humid environment. Luminous road marking paint is exposed to the outdoors and subjected to long-term exposure to sunlight and erosion by rain, which will cause it to fade and age and decompose, resulting in weakened performance of the luminescent paint. In order to solve the above problems, the present invention limits the fineness of strontium aluminate long afterglow luminescent powder to 100-400 meshes. The particle size of strontium aluminate long afterglow luminescent powder in this fineness range is appropriate, which can reduce the agglomeration phenomenon when the raw materials are mixed, and improve dispersibility and compatibility. In addition to acting as a film-forming aid in the coating, the alcohol ester twelve in the raw material of the present invention also produces a synergistic effect with gas-phase silica to improve the surface wettability of the strontium aluminate long afterglow luminescent powder and reduce the interfacial tension. Combined with the preparation method of the coating of the present invention, the luminescent material is wrapped by film-forming substances and additives such as fillers to form a dense thin layer, which isolates the external moisture and prevents the luminescent material from being destroyed inside. At the same time, it does not come into direct contact with water, so the coating has good water resistance, which can effectively improve the poor water resistance of the strontium aluminate long afterglow luminescent powder, and the problem that the luminescent intensity decreases due to a hydrolysis reaction when in contact with water or in a humid environment.

[0016] The second technical solution of the present invention:

[0017] The present invention also provides a method for preparing the long afterglow luminous road marking paint suitable for road engineering, comprising the following steps:

[0018] (1) Accurately weigh each raw material according to mass percentage;

[0019] (2) Add 1 / 2 of the anti-settling agent to the silicone-acrylic emulsion and stir for 10 to 15 minutes;

[0020] (3) Mix the remaining 1 / 2 of the anti-settling agent with the luminescent material, glass powder and titanium dioxide, add it to the substance obtained in step (2), and stir for 25 to 30 minutes;

[0021] (4) Add a defoaming agent, a leveling agent and a film-forming aid to the substance obtained in step (3), and stir for 5 to 10 minutes to obtain the long afterglow luminous road marking paint suitable for road engineering.

[0022] Preferably, in the preparation method of the long afterglow luminescent road marking paint suitable for road engineering, the luminescent material and titanium dioxide are sieved separately using a laboratory standard sieve to obtain the required fineness.

[0023] Preferably, in the preparation method of the long afterglow luminescent road marking paint suitable for road engineering, the raw materials are mixed at room temperature (25±2° C.).

[0024] The third technical solution of the present invention:

[0025] The present invention also provides the application of the long afterglow luminous road marking paint suitable for road engineering in road engineering.

[0026] Preferably, the coating thickness of the long afterglow luminous road marking paint suitable for road engineering is 600μm when used. Since the coating thickness has a certain influence on the luminous brightness, when the coating thickness is moderate, the luminescent material in the coating can achieve the best utilization rate, fully absorb the external light source, and produce a good luminous effect. However, as the coating thickness increases, the obstruction of light by film-forming substances, luminescent materials and fillers increases, and the luminescent material at the bottom of the coating cannot fully absorb the external light source, resulting in a decrease in the contribution of the luminescent material at the bottom to the initial brightness of the coating, further resulting in the initial brightness of the coating no longer continuing to increase or a small increase. After the coating thickness exceeds 600μm, the initial brightness of the coating increases less, so when the coating thickness is 600μm, the utilization rate of the luminescent material is high, and the recommended coating thickness is 600μm.

[0027] The fourth technical solution of the present invention:

[0028] The present invention also provides a design method for the long afterglow luminous road marking paint suitable for road engineering, which adopts the entropy weight method (Topsis method) and includes the following steps:

[0029] (1) Design the level corresponding to the raw materials of long afterglow luminous road marking paint suitable for road engineering, and select a suitable orthogonal table according to the number of factors and levels;

[0030] (2) preparing the long afterglow luminous road marking paint suitable for road engineering according to the orthogonal test design scheme, and testing the test indicators of the long afterglow luminous road marking paint suitable for road engineering;

[0031] (3) Using the entropy weight method theory, the amount of information of each indicator is determined by analyzing the observed values ​​of the indicators. Combined with the results of the orthogonal test, the weight of each indicator is calculated to provide a basis for the comprehensive evaluation of multiple indicators.

[0032] (4) First, a weighted decision matrix is ​​constructed according to the weights of the indicators. Then, the positive and negative ideal solutions are determined, and the Euclidean distances from the evaluation object to the positive and negative ideal solutions are calculated. Finally, the proximity of each test scheme to the most ideal scheme is calculated, and the schemes are sorted according to the proximity, so as to realize the selection of the optimal ratio of the long afterglow luminous road marking paint suitable for road engineering.

[0033] Preferably, in the design method of the long afterglow luminous road marking paint suitable for road engineering, in step (1), the mass percentage of the luminescent material, glass powder and titanium dioxide in the long afterglow luminous road marking paint suitable for road engineering is taken as factors A, B and C respectively, and three levels are designed for each factor. 4 ) Design of experiments;

[0034] The test indicators of the long afterglow luminous road marking paint suitable for road engineering described in step (2) include initial brightness, 10min brightness, afterglow time and brightness factor.

[0035] Preferably, in the design method of the long afterglow luminous road marking paint suitable for road engineering, step (3) specifically includes:

[0036] The index weights were determined using the Topsis method, the original data matrix was established using the orthogonal test results, and the data was standardized to eliminate the differences between the indicators.

[0037] Based on the standardized data, the entropy value of the indicator and the information entropy redundancy are calculated, and then the weights of the four indicators, namely initial brightness, 10-minute brightness, afterglow time and brightness factor, are determined.

[0038] Preferably, in the design method of the long afterglow luminous road marking paint suitable for road engineering, step (4) specifically includes:

[0039] The Topsis method is used for comprehensive evaluation, and the weighted decision matrix is ​​constructed by combining the indicator weights obtained in step (3). Secondly, the positive ideal and negative ideal solutions are determined;

[0040] Calculate the Euclidean distance from the evaluation object to the positive and negative ideal solutions, and finally calculate the proximity of each test solution to the most ideal solution, and sort them by proximity.

[0041] After determining the optimal ratio of long afterglow luminous road marking paint suitable for road engineering, its performance (water resistance, alkali resistance, non-stick tire drying time, wear value, anti-skid value, bonding strength and color difference value after stain resistance) was tested.

[0042] The present invention adopts the orthogonal test-Topsis method to select the optimal ratio of the long afterglow luminous paint, thereby improving the accuracy and scientificity of the selection of the ratio of the long afterglow luminous paint, and verifies the road performance of the optimal ratio. The long afterglow luminous road marking paint of the present invention has good luminous performance and road performance, can be used for road markings at night to guide sight and ensure driving safety, and has the advantages of simple preparation method and easy control, which is conducive to popularization and application.

[0043] Compared with the prior art, the present invention has the following advantages and technical effects:

[0044] 1. In the long afterglow luminous road marking paint suitable for road engineering of the present invention, strontium aluminate long afterglow luminescent powder is selected as the luminescent light source, and the silicone acrylic emulsion used is a bluish white emulsion with good light transmittance and excellent adhesion; glass powder and rutile titanium dioxide can improve the brightness and road performance of the long afterglow luminous road marking paint, and reduce the cost. The long afterglow luminous road marking paint of the present invention has good luminous performance and road performance, and can be used in road engineering.

[0045] 2. When preparing long afterglow luminous road marking paint, the present invention improves the surface wettability of the strontium aluminate long afterglow luminescent powder and reduces the interfacial tension by controlling the fineness of the strontium aluminate long afterglow luminescent powder and adding fumed silica and alcohol ester twelve during the preparation process of the paint. Combined with the preparation method of the paint of the present invention, the luminescent material is wrapped by additives such as film-forming substances and fillers to form a dense thin layer, which isolates the external moisture and prevents the luminescent material from being destroyed inside. At the same time, it does not come into direct contact with water, so the water resistance of the coating is good, which can effectively improve the poor water resistance of the strontium aluminate long afterglow luminescent powder, and the problem that the luminescent intensity decreases due to hydrolysis reaction when in contact with water or in a humid environment.

[0046] 3. The present invention adopts the orthogonal test-Topsis method to select the optimal ratio of long afterglow luminous road marking paint, which not only reduces the number of experiments and improves the test efficiency, but also avoids the defect of relying on subjective analysis when considering multiple indicators comprehensively, and improves the accuracy and scientificity of the selection of the ratio of long afterglow luminous road marking paint.

[0047] 4. The long afterglow luminous road marking paint of the present invention has the advantages of simple preparation method and easy control, which is conducive to popularization and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0049] Figure 1is the afterglow decay curve of the coating with a thickness of 200 to 700 μm (200 μm, 300 μm, 400 μm, 500 μm, 600 μm and 700 μm) in Example 1;

[0050] Figure 2 This is a real picture of the coating plate before immersion (the coating prepared in Example 2 is coated on the asbestos plate with a thickness of 600 μm);

[0051] Figure 3 This is a real picture of the coating plate after immersion (the coating prepared in Example 2 is coated on the asbestos plate with a thickness of 600 μm). DETAILED DESCRIPTION

[0052] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0053] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0054] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0055] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0056] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0057] In the present invention, the test standards of the coating are as follows:

[0058] (1) Status in the container

[0059] According to the test of "Road Marking Paint" JT / T280-2022, after opening the package, the water-based paint should be in a good state without lumps and skins, and should be easy to stir. After stirring, the color of the paint is uniform, without obvious color difference or mottled phenomenon.

[0060] (2) Coating appearance

[0061] Apply the paint on the cement asbestos board and after drying for 24 hours, observe whether the coating is uniform, whether there is blistering, cracking, or falling off, and whether the color is uniform.

[0062] (3) Water resistance

[0063] As road marking paint is exposed to the elements all year round, it may rain and the markings may be soaked in water. Therefore, it is necessary to consider the coating's resistance to water immersion. According to the "Water Resistance of Paint Film" GB / T 1733, the changes in the coating after 24 hours of immersion in water are observed, and the changes in brightness before and after immersion are tested.

[0064] (4) Alkali resistance

[0065] According to the GB / T9265 test of "Determination of Alkali Resistance of Architectural Coatings", the surface changes of the coating after immersion in a saturated solution of calcium hydroxide were visually observed. At the same time, the brightness comparison before and after the alkali resistance test was tested.

[0066] (5) Freeze-thaw stability

[0067] The test is carried out in accordance with "Road Marking Paint" JT / T280-2022. After being placed at -5±2℃ for 18 hours, it is immediately placed at 23±2℃ for 6 hours. This is one cycle. After three cycles, there should be no caking or crusting, and it should be easy to stir.

[0068] (6) Non-stick tire drying time

[0069] According to the test of "Road Marking Paint" JT / T280-2022, the drying time of water-based non-stick tire marking should be less than 15 minutes.

[0070] (7) Stain resistance test

[0071] In order to comprehensively judge the anti-fouling property of the luminescent coating, the initial brightness decrease rate and the color difference value ΔE were used as evaluation indicators.

[0072] The anti-fouling property of the luminescent coating is calculated according to formulas 2.2 and 2.3:

[0073]

[0074] Where X is the initial brightness decrease rate of the luminous coating, %; A is the initial brightness of the coating before the stain resistance test, cd / m 2 ; B is the initial brightness of the coating after the stain resistance test, cd / m 2 .

[0075]

[0076] Among them, ΔE is the color difference value, L is the brightness value, a is the red-green value, b is the yellow-blue value, L0, a0, b0 are the color parameters of the coating before the pollution resistance test, and L1, a1, b1 are the color parameters of the coating after the pollution resistance test.

[0077] Among them, the smaller ΔE is, the closer the color of the stain is to the uncontaminated coating, which can more intuitively reflect the color change before and after the coating contamination test.

[0078] (8) UV aging test

[0079] Long afterglow luminous road marking paint is exposed to the natural environment and ages under the action of sunlight, oxygen and water. However, the aging cycle of paint under natural conditions is relatively long, so the aging of paint under natural conditions is simulated in the laboratory. The test is carried out using a BR-4000 xenon lamp weathering test chamber with a radiation intensity of 0.51W / m 2 , irradiated at 60℃ for 8h, cooled at 50℃ in the dark for 4h, accelerated aging cycles of 300h, 400h and 500h, UV aging test was carried out according to "Artificial climate accelerated test method for plastic and rubber materials for mechanical industrial products" GB / T 14522-2008. The test indicators are the initial brightness reduction rate, color difference and wear value before and after aging. The initial brightness reduction rate and color difference value are calculated according to formulas 2.2 and 2.3.

[0080] All raw materials used in the embodiments of the present invention are purchased from the market or synthesized from literature. As an example, the silicone-acrylic emulsion was purchased from Zhaoqing Xinguangli Chemical Industry Co., Ltd. It is a bluish-white emulsion with a solid content of 47±1wt%, a viscosity of 200-800mPa·s, and a pH of 8. The luminescent material is SrAl2O4:Eu with a fineness of 100-400 mesh. 2+ ,Dy 3+ , the luminescent color is yellow-green, according to the literature Rojas-Hernandez RE, Rubio-Marcos F, Rodriguez M et al. Long-lasting phosphors: SrAl2O4: Eu, Dy as the most studied material[J]. Renewable and Sustainable Energy Reviews, 2018, 81: 2759-2770. Synthesis. The main component of rutile titanium dioxide is TiO2, which is a white powder with a density of 4.2-4.3 g·cm -3 , Mohs hardness is 6 to 6.5. The film-forming additive is alcohol ester twelve, the leveling agent is a water-based leveling agent - BYK-333 leveling agent, the defoamer is a silicone defoamer, and the anti-settling agent is fumed silica. The physical properties of each additive are shown in Table 1.

[0081] Table 1 Physical properties of additives

[0082]

[0083] In the present invention, "%" means "mass percentage" unless otherwise specified.

[0084] The technical solution of the present invention is further illustrated by the following embodiments.

[0085] Example 1

[0086] The raw materials and proportions of long afterglow luminous road marking paint are optimized based on the Topsis method:

[0087] Step 1, design the levels corresponding to the raw materials of long afterglow luminous road marking paint, and select a suitable orthogonal table according to the number of factors and levels.

[0088] Select the luminescent materials (SrAl2O4:Eu 2+ ,Dy 3+ ), glass powder (fineness of 1000-2000 mesh), titanium dioxide (rutile titanium dioxide) accounted for the mass percentage of long afterglow luminous road marking paint as factors A, B, and C. Each factor was designed with three levels. According to the orthogonal table L9 (3 4 ) Experiment design is shown in Table 2.

[0089] Table 2 Factor level table

[0090]

[0091] Step 2: prepare a long afterglow luminous road marking paint according to an orthogonal experimental design scheme, and test the indicators of the long afterglow luminous road marking paint.

[0092] The coating thickness of the long afterglow luminous road marking paint is 600μm; referring to "JG / T446-2014 Energy Storage Luminous Paint for Buildings" and "JT / T280-2022 Road Marking Paint", the brightness, 10min brightness, afterglow time and brightness factor of the long afterglow luminous road marking paint are tested, and the test results are shown in Table 3.

[0093] Table 3 Long afterglow luminous coating test results

[0094]

[0095]

[0096] Step 3, use the Topsis method to determine the indicator weights, establish the original data matrix with the orthogonal test results, and standardize the data to eliminate the differences between indicators. Based on the standardized data, calculate the entropy value of the indicator and the information entropy redundancy, and then determine the weights of the four indicators of initial brightness, 10min brightness, afterglow time and brightness factor.

[0097] The specific process is:

[0098] (1) Establish a data matrix. Assuming that the evaluation scheme is n and the evaluation index is m, the original matrix is:

[0099]

[0100] where x ij Represents the value of the jth indicator in the i-th solution.

[0101] (2) Data standardization:

[0102]

[0103] (3) Calculate the proportion of the i-th option to the j-th indicator:

[0104]

[0105] Where i=1, 2,…, n; j=1, 2,…, m.

[0106] (4) Calculate the entropy value e of the jth indicator j :

[0107] d j =1-e j ,j=1,L,m

[0108] in: Meet e j >1

[0109] (5) Calculate the information entropy redundancy:

[0110] d j =1-e j ,j=1,L,m

[0111] (6) Calculate the weight of each indicator:

[0112]

[0113] The weight calculation results of each indicator are shown in Table 4.

[0114] Table 4 Index weight values

[0115]

[0116] Step 4: First, use the Topsis theory and the indicator weights obtained in step (3) to construct a weighted decision matrix; second, determine the positive and negative ideal solutions, calculate the Euclidean distance from the evaluation object to the positive and negative ideal solutions, and finally calculate the proximity of each experimental solution to the most ideal solution and sort them according to the proximity.

[0117] The specific process is:

[0118] (1) According to the indicator weights determined by the entropy weight method, a weighted decision matrix Y = (y ij ) m×n

[0119]

[0120] (2) Determine the positive ideal solution and the negative ideal solution

[0121] Positive ideal solution and negative ideal solution They are weighted decision matrices Y=(y ij ) m×n After calculation, the positive ideal solution of initial brightness is 0.4090431, and the negative ideal solution is 0.2310625; the positive ideal solution of 10min brightness is 0.3959193, and the negative ideal solution is 0.2500542; the positive ideal solution of afterglow time is 0.3677300, and the negative ideal solution is 0.2860122; the positive ideal solution of brightness factor is 0.3447932, and the negative ideal solution is 0.3205880.

[0122] (3) Calculate each experimental scheme to the positive ideal solution and negative ideal solution The Euclidean distance and

[0123]

[0124] (4) Calculate the CI of each experimental scheme

[0125]

[0126] The larger the CI, the better the experimental scheme. The experimental schemes are ranked according to the CI values, as shown in Table 5.

[0127] Table 5 Ranking index values ​​of each sample

[0128]

[0129] From the ranking of each scheme, it can be seen that No. 5 is the optimal choice for the ratio of long afterglow luminous road marking paint, that is, luminous material 25%, glass powder 8%, titanium dioxide 2%, silicone acrylic emulsion 60.4%, anti-settling agent 0.6%, film-forming aid 2.4%, defoaming agent 0.8%, and leveling agent 0.8%.

[0130] Example 2

[0131] The raw materials of the long afterglow luminous road marking paint suitable for road engineering in this embodiment are as follows:

[0132] Luminescent material (SrAl2O4:Eu 2+ ,Dy 3+ , fineness is 100-400 mesh) 25%, glass powder (fineness is 1000-2000 mesh) 8%, titanium dioxide (rutile titanium dioxide) 2%, silicone acrylic emulsion (viscosity is 200-800mPa·s) 60.4%, anti-settling agent (fumed silica) 0.6%, film-forming aid (alcohol ester twelve) 2.4%, defoaming agent 0.8%, leveling agent 0.8%.

[0133] The preparation method of the long afterglow luminous road marking paint suitable for road engineering is as follows:

[0134] Weigh the luminescent material, glass powder, titanium dioxide, and fumed silica in proportion (before mixing the raw materials, use a laboratory standard sieve to sieve the luminescent material and titanium dioxide separately to obtain the required fineness), and weigh the silicone-acrylic emulsion at the same time. Add the silicone-acrylic emulsion into a beaker at room temperature and stir, then add 1 / 2 of the weighed fumed silica and stir for 12 minutes;

[0135] The remaining 1 / 2 of the fumed silica is uniformly mixed with the luminescent material, glass powder, and titanium dioxide, and is added slowly and evenly, and stirred for 28 minutes until the raw materials are completely and evenly dispersed in the emulsion to form a uniform mixture;

[0136] The defoamer, leveling agent and film-forming aid were added in sequence and stirred for 8 minutes to finally obtain a long afterglow luminous road marking paint suitable for road engineering with an initial brightness of 3.93 cd / m 2The luminous flux is 6.6717lm, and the chromaticity coordinates are concentrated in the yellow-green area. The luminescence mechanism of long afterglow luminous road markings is explained by excitation spectrum and emission spectrum. Eu 2+ The transition of electrons in it causes it to emit light.

[0137] In order to explore the coating thickness under the best luminous effect, 6 different thicknesses are set. In combination with the "Quality Requirements and Test Methods for Road Traffic Markings" GBT 16311-2009, the thickness is set to 200-700μm (200μm, 300μm, 400μm, 500μm, 600μm and 700μm). Taking the coating prepared in this embodiment as an example, the coatings of the above 6 thicknesses are applied on the asbestos board to test the luminous brightness. The afterglow decay curve is shown in the figure. Figure 1 As shown. It can be seen that the attenuation trend of the luminous brightness of luminous coatings with different coating thicknesses within 20 minutes is basically the same. The initial brightness increases with the increase of coating thickness. When the thickness increases to a certain value, the luminous brightness increases slowly. When the coating thickness is 200μm, the initial brightness is 2.35cd / m 2 , the initial brightness of 200-700μm is 2.35cd / m 2 , 2.67cd / m 2 , 3.12cd / m 2 , 3.21cd / m 2 , 3.63cd / m 2 , 3.82cd / m 2 , with the increase of coating thickness, the brightness continues to increase. The coating thickness of 600μm and 700μm increases by 54.5% and 62.6% compared with 200μm, which is a large increase. However, when the coating thickness is 600μm, it increases by 13.1% compared with the coating thickness of 500μm, while the coating thickness of 700μm only increases by 5.2% compared with the coating thickness of 600μm. The coating thickness has a certain influence on the luminous brightness. When the coating thickness is moderate, the luminescent material in the coating can achieve the best utilization rate, fully absorb the external light source, and produce a good luminous effect. However, with the increase of coating thickness, the film-forming material, luminescent material and filler have an enhanced obstruction effect on light, and the luminescent material at the bottom of the coating cannot fully absorb the external light source, resulting in a decrease in the contribution of the luminescent material at the bottom to the initial brightness of the coating, which further causes the initial brightness of the coating to no longer continue to increase or increase slightly. After the coating thickness exceeds 600μm, the initial brightness of the coating increases less, so when the coating thickness is 600μm, the utilization rate of the luminescent material is higher, and the recommended coating thickness is 600μm.

[0138] Comparative Example 1

[0139] The same as Example 2, except that the silicone acrylic emulsion is silicone acrylic emulsion 8912 purchased from Qingdao Gudao Technology Co., Ltd., with a solid content of 45 wt % and a viscosity of 1000-5000 mPa·s.

[0140] Comparative Example 2

[0141] Same as Example 2, except that the film-forming aid is propylene glycol butyl ether.

[0142] The performance verification was carried out based on the long afterglow luminous road marking paint suitable for road engineering prepared in Example 2:

[0143] According to "Road Marking Paint" JT / T280-2022 and "Measurement Method of Paint Film Color" GB / T 11186.3, various indicators of long afterglow luminous road marking paint were tested. The test results are shown in Table 6.

[0144] Table 6 Long afterglow luminous road marking paint test results

[0145]

[0146]

[0147] The water resistance of the coatings of Example 2, Comparative Example 1 and Comparative Example 2 was tested in accordance with the provisions of GB / T 1733 on Water Resistance of Paint Films. The test showed that the coating prepared in Example 2 had no abnormal water resistance for 96 hours, no blistering, no peeling and no discoloration; the coating prepared in Comparative Example 1 had no abnormal water resistance for 24 hours, no blistering, no peeling and no discoloration; the coating prepared in Comparative Example 2 had no abnormal water resistance for 24 hours, no blistering, no peeling and no discoloration; the light resistance of the coatings of Example 2, Comparative Example 1 and Comparative Example 2 was tested, the samples were placed under a high-pressure mercury lamp and irradiated continuously for 72 hours, and the appearance color changes of the coatings before and after irradiation were compared. The test showed that the coating of Example 2 had no abnormality, and the coatings of Comparative Example 1 and Comparative Example 2 had slight discoloration to varying degrees.

[0148] The luminescent material (SrAl2O4:Eu 2+ ,Dy 3+ ) and deionized water in a mass ratio of 1:20 (2 g of luminescent material, 40 g of deionized water), the luminescent material was soaked in deionized water, the pH value was tested, and the luminescent material was dried after soaking for 24 hours for afterglow detection. It was found that during the soaking process, SrAl2O4:Eu 2+ ,Dy 3+ The pH value of the solution changes from 7.76 to 11.33, and the solution becomes alkaline. This is because SrAl2O4:Eu 2+ ,Dy 3+The luminescent powder was hydrolyzed to generate Al(OH)3 precipitate; after immersion in water, SrAl2O4:Eu 2+ ,Dy 3+ The brightness of the luminescent powder also decays significantly, from 14.69cd / m 2 Attenuation to 7.87cd / m 2 , so SrAl2O4:Eu 2+ ,Dy 3+ The water resistance of luminescent powder is poor.

[0149] According to the determination method of "Water resistance of paint film" GB / T 1733, after immersion, the coating plate (the coating prepared in Example 2 was coated on the asbestos plate with a thickness of 600 μm, and two groups of experiments were carried out in parallel) was inspected. Figure 2 and Figure 3 It was found that the long afterglow luminescent coating did not change color, bubble, wrinkle, or fall off after immersion, which proved that the coating of the present invention solved the problem of SrAl2O4:Eu 2+ ,Dy 3+ The problem of poor water resistance of luminescent powder.

[0150] The brightness of the coating (i.e., the coating prepared in Example 2 was coated on the asbestos board with a thickness of 600 μm, the same below) was tested before and after immersion in water. It was found that the initial brightness of the coating increased from 1.6 cd / m 2 Reduced to 1.56cd / m 2 , the change is small. After the light source is removed for 300s, 600s, 900s, and 1200s, the brightness before and after immersion is almost unchanged, proving that the coating prepared by the coating of the present invention has good water resistance. As the immersion time of the coating increases, the initial brightness decreases slightly, and the brightness of the coating decreases by only 0.12cd / m after immersion for 7 days. 2 After long-term immersion in water, the brightness decreases less, which also proves that the coating has good water resistance. This is because the luminescent material is wrapped by film-forming substances and fillers and other additives to form a dense thin layer, which isolates the external moisture and keeps the luminescent material from being damaged inside. At the same time, it does not come into direct contact with water, so the coating has good water resistance.

[0151] In addition, the initial brightness reduction rate and color difference of the above-mentioned coating after being contaminated by dust and oily pollutants were tested through the stain resistance test. The initial brightness reduction rate was below 10%, and the color difference value was less than 2; the abrasion value after aging for 500 hours was 23.5 mg, that is, the brightness, chromaticity and wear resistance of the coating after UV aging were excellent and can be used normally.

[0152] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A long afterglow luminous road marking paint suitable for road engineering, characterized in that: Calculated by mass percentage, the raw materials include: 20-30% luminescent material, 4-8% glass powder, 2-6% titanium dioxide, 0.6% anti-settling agent, 2.4% film-forming aid, 0.8% defoaming agent, 0.8% leveling agent, and the balance is silicone acrylic emulsion.

2. The long afterglow luminous road marking paint suitable for road engineering according to claim 1, characterized in that: The luminescent material is strontium aluminate long afterglow luminescent powder, and the fineness of the strontium aluminate long afterglow luminescent powder is 100-400 meshes.

3. The long afterglow luminous road marking paint suitable for road engineering according to claim 1, characterized in that: The glass powder has a fineness of 1000-2000 meshes.

4. The long afterglow luminous road marking paint suitable for road engineering according to claim 1, characterized in that: The viscosity of the silicone-acrylic emulsion is 200-800 mPa·s.

5. The long afterglow luminous road marking paint suitable for road engineering according to claim 1, characterized in that: The anti-settling agent is fumed silica, the film-forming aid is alcohol ester dodecahydrate, the defoaming agent is an organosilicon defoaming agent, and the leveling agent is a water-based leveling agent.

6. A method for preparing a long afterglow luminous road marking paint suitable for road engineering according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Accurately weigh each raw material according to mass percentage; (2) Add 1 / 2 of the anti-settling agent to the silicone-acrylic emulsion and stir for 10 to 15 minutes; (3) Mix the remaining 1 / 2 of the anti-settling agent with the luminescent material, glass powder and titanium dioxide, add it to the substance obtained in step (2), and stir for 25 to 30 minutes; (4) Add a defoaming agent, a leveling agent and a film-forming aid to the substance obtained in step (3), and stir for 5 to 10 minutes to obtain the long afterglow luminous road marking paint suitable for road engineering.

7. Use of the long afterglow luminous road marking paint suitable for road engineering as claimed in any one of claims 1 to 5 in road engineering.

8. The use according to claim 7, characterized in that: The coating thickness of the long afterglow luminous road marking paint suitable for road engineering is 600 μm when used.

9. A design method for a long afterglow luminous road marking paint suitable for road engineering according to any one of claims 1 to 5, characterized in that: The entropy weight method is adopted, which includes the following steps: (1) Design the level corresponding to the raw materials of long afterglow luminous road marking paint suitable for road engineering, and select a suitable orthogonal table according to the number of factors and levels; (2) preparing the long afterglow luminous road marking paint suitable for road engineering according to the orthogonal test design scheme, and testing the test indicators of the long afterglow luminous road marking paint suitable for road engineering; (3) Using the entropy weight method theory, the amount of information of each indicator is determined by analyzing the observed values ​​of the indicators. Combined with the results of the orthogonal test, the weight of each indicator is calculated to provide a basis for the comprehensive evaluation of multiple indicators. (4) First, a weighted decision matrix is ​​constructed according to the weights of the indicators. Then, the positive and negative ideal solutions are determined, and the Euclidean distances from the evaluation object to the positive and negative ideal solutions are calculated. Finally, the proximity of each test scheme to the most ideal scheme is calculated, and the schemes are sorted according to the proximity, so as to realize the selection of the optimal ratio of the long afterglow luminous road marking paint suitable for road engineering.

10. The design method of the long afterglow luminous road marking paint suitable for road engineering according to claim 9, characterized in that: In step (1), the mass percentage of luminescent material, glass powder and titanium dioxide in the long afterglow luminescent road marking paint suitable for road engineering is taken as factors A, B and C respectively, and three levels are designed for each factor. 4 ) Design of experiments; The test indicators of the long afterglow luminous road marking paint suitable for road engineering described in step (2) include initial brightness, 10min brightness, afterglow time and brightness factor.

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