Water-based marking environment-friendly coating with low color interference and high stability and production method thereof

Abstract

The invention discloses a low-color-interference high-stability water-based marking environment-friendly coating and a production method thereof, and relates to the technical field of curing coatings. The invention discloses a low-color-interference high-stability water-based marking environment-friendly coating. The coating is prepared from the following components in parts by mass: 40-60 parts of base resin, 30-40 parts of wear-resistant filler, 0.5-1.5 parts of a dispersing agent, 0.1-0.5 part of a defoaming agent, 1-3 parts of a coalescing agent, 0.1-0.5 part of a thickening agent, 1-3 parts of an anti-freezing agent, 0.5-2 parts of an antioxidant and 10-20 parts of deionized water. By adding the antioxidant with a specific structure, the problems of discoloration, aging and the like caused by oxidation of the coating are effectively inhibited, the service life of the coating is remarkably prolonged, and the attractiveness and functional stability of marked lines are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of curing paint, in particular to a low-color-interference high-stability water-based marking environmental protection paint and a production method thereof. BACKGROUND

[0002] With the rapid development of urban traffic, the demand for road marking paint is increasing. Traditional marking paint is mostly solvent-based, which has high volatile organic compound content, causing great harm to the environment and human health, such as air pollution, respiratory irritation, etc. At the same time, these paints also have shortcomings in stability, wear resistance and weather resistance, etc., and are difficult to meet the requirements of modern traffic for high stability and long service life of road marking paint.

[0003] Water-based marking paint has gradually attracted attention due to its environmental protection, low volatile organic compound emission, etc. However, the existing water-based marking paint still has some problems. For example, its film-forming performance is poor, resulting in slow drying speed of the paint after construction, affecting the road traffic efficiency; the adhesion is insufficient, which is easy to fall off under frequent vehicle rolling, reducing the clarity and service life of the marking; in low temperature environment, it is easy to have freeze-cracking phenomenon, affecting the normal use of the paint.

[0004] In addition, the traditional water-based marking paint also has defects in oxidation resistance, which is easy to discolor and age due to oxidation, reducing the aesthetic and functional properties of the paint. Therefore, it has become an urgent task for the paint industry to develop a low-color-interference high-stability water-based marking environmental protection paint to solve the problems of the existing water-based marking paint in stability, wear resistance, weather resistance, etc., while meeting the environmental protection requirements. SUMMARY

[0005] The purpose of the present application is to solve the problems of poor film-forming performance, insufficient adhesion and poor weather resistance of the existing water-based marking paint, and to provide a high-stability water-based marking environmental protection paint with high adhesion and strong weather resistance and a production method thereof.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present application is: a low-color-interference high-stability water-based marking environmental protection paint, which is made of the following components by mass fraction: base resin: 40-60 parts, wear-resistant filler: 30-40 parts, dispersing agent: 0.5-1.5 parts, defoaming agent: 0.1-0.5 parts, film-forming aid: 1-3 parts, thickening agent: 0.1-0.5 parts, anti-freezing agent: 1-3 parts, antioxidant: 0.5-2 parts, deionized water: 10-20 parts. The antioxidant is a compound shown in Formula 1: Formula 1: ; R1 in Formula 1 is a substituent, and R1 is selected from: methyl, amino, hydroxyl, methoxy, nitro.

[0007] Further, the base resin is one or more of epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin.

[0008] Further, the wear-resistant filler is one or more of titanium white powder, silicon powder, glass microbeads.

[0009] Further, the dispersant is one or more of sodium diisooctyl sulfosuccinate or sodium dodecyl polyoxyethylene ether sulfate.

[0010] Further, the defoaming agent is one or more of BYK-024, BYK-028, Tego-810.

[0011] Further, the film-forming aid is one or more of alcohol ester dodecane, dipropylene glycol butyl ether.

[0012] Further, the thickening agent is Rongmenhasi RM-8W.

[0013] Further, the antifreeze agent is ethylene glycol.

[0014] Further, the antioxidant is any one of the following compounds: ; ; .

[0015] The production method of low-color interference high-stability water-based marking environmentally friendly paint comprises the following steps: (1) Pre-dispersion stage: the deionized water and the dispersant are added to a high-speed disperser, and stirred at a speed of 300-500 r / min for 5-8 minutes until the dispersant is completely dissolved; then the wear-resistant filler is added, the temperature is raised to 25-30°C, and the stirring speed is adjusted to 1000-1500 r / min for high-speed dispersion for 15-30 minutes until the system fineness is ≤50 μm, to obtain a pre-dispersion slurry; (2) Resin mixing stage: the stirring speed of the high-speed disperser is reduced to 500-800 r / min, the base resin is added to the pre-dispersion slurry, and the stirring is continued for 10-20 minutes to ensure uniform mixing of the resin and the slurry; (3) Additive addition stage: keep the stirring speed at 500-800 r / min, and add the defoaming agent, film-forming aid, antifreeze agent, and antioxidant in sequence, stir for 3-5 minutes after adding each additive, and continue stirring for 8-15 minutes after all the additives are added; (4) Viscosity adjustment and filtration stage: add the thickening agent, and stir at a speed of 500-800 r / min for 5-10 minutes; finally, filter with a 100-200 mesh filter screen to remove undispersed particles and impurities, and obtain the low-color interference high-stability water-based marking environmentally friendly paint.

[0016] Further, the step (1) in high speed dispersion process is cooled by circulating water, and the system temperature is maintained at not more than 30 DEG C.

[0017] Further, the step (4) is filtered by 150 mesh nylon filter screen, and the coating is placed at 20-25 DEG C for 10-20 minutes after filtration to remove the residual micro-bubbles in the system.

[0018] The antioxidant mechanism of the application is to interrupt the free radical chain reaction, delay or inhibit the oxidative degradation process of the coating matrix resin, mainly through hydrogen supply and free radical capture mechanism. The phenolic hydroxyl group in the molecular structure is the key active site for the antioxidant effect. During the use of the coating, the resin molecular chain will produce active free radicals under the influence of oxygen, heat, ultraviolet light and other factors. These free radicals will take away the hydrogen atoms on other resin molecules, trigger a chain reaction, cause polymer chain rupture and crosslinking, and thus cause the coating film to appear problems such as powdering and discoloration. The phenolic hydroxyl group in the antioxidant molecule can provide an active hydrogen atom to the peroxy radical, making it generate stable hydroperoxide, and itself form a phenoxy radical. The phenoxy radical is very stable due to the electron-donating effect and steric hindrance effect of the ortho substituent, and cannot continue to initiate chain reaction, thus effectively terminating the growth of the oxidation chain. In addition to providing hydrogen atoms, the stable phenoxy radical can also combine with another active radical to generate a more stable non-radical product, thus consuming more free radicals. In addition, the substituents in the antioxidant molecule can form steric hindrance to protect the active groups from being consumed prematurely, and at the same time avoid ineffective reactions of antioxidant radicals with other molecules.

[0019] The present application aims at the problems of poor film formation, slow drying, insufficient wear resistance, poor weather resistance, easy to freeze crack and anti-oxidation defects of existing water-based marking paint, and realizes performance improvement through the synergistic effect of each component. As the core, the base resin improves the film formation density and adhesion, and accelerates the drying speed; the fluorosilicon emulsion gives the coating weather resistance and water resistance, and solves the problems of poor film formation and slow drying, and lays the foundation for weather resistance. The wear-resistant filler is filled in the resin matrix to enhance the hardness and anti-rolling property of the coating, and cooperates with the dispersion effect of the dispersing agent to avoid filler agglomeration, so that the filler is uniformly distributed, and the wear resistance is further improved to solve the problem of vehicle rolling wear. The defoaming agent eliminates the bubbles generated during preparation and construction to avoid coating pores and ensure the density and wear resistance; the film forming aid assists the resin to form a film at low temperature, and cooperates with the antifreeze agent to prevent low-temperature freeze cracking, and the film forming aid improves the low-temperature film forming efficiency to solve the problems of low-temperature freeze cracking and film formation. The thickening agent adjusts the viscosity of the system to ensure the construction property and uniformity of the coating thickness, and ensures the stable performance; the specific structure antioxidant delays the oxidation aging of the resin by interrupting the free radical chain reaction, and solves the problem of oxidation discoloration in combination with the weather resistance of the fluorosilicon emulsion; the deionized water as the carrier ensures the uniform mixing of each component and provides the basis for the synergistic effect. Each component is targeted and complementary to form a complete synergistic system with multiple effects, and the performance of the coating is improved comprehensively.

[0020] Compared with the prior art, the present application has the following advantages: 1. The comprehensive performance is significantly improved: by optimizing the ratio and synergistic effect of key components such as base resin, wear-resistant filler and film forming aid, the film formation performance, wear resistance, weather resistance and low-temperature freeze cracking resistance of the present application are significantly improved, and the problems of slow drying speed, insufficient wear resistance and poor weather resistance of existing water-based marking paint are solved.

[0021] 2. The environmental benefits are obvious: based on the water-based system, the emission of volatile organic compounds is reduced, the harm of traditional solvent-based paint to the environment and human health is reduced, and the development trend of green paint is met.

[0022] 3. The oxidation resistance and stability are enhanced: by adding an antioxidant with a specific structure, the present application effectively inhibits the discoloration and aging of the coating caused by oxidation, significantly prolongs the service life of the coating, and improves the appearance and functional stability of the marking. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The nuclear magnetic chart of the antioxidant 1 described in the present application. DETAILED DESCRIPTION

[0024] The technical solutions of the present application will be clearly and completely described below with reference to the drawings in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of the present application.

[0025] Synthesis Example 1: Synthesis of antioxidant 1: Into a dry reactor, 10.00 g of compound 1, 7.07 g of compound 2 and 150 ml of tetrahydrofuran were sequentially added, stirred until uniformly dispersed, then 2.05 g of concentrated sulfuric acid was slowly added dropwise, heated to 80℃, and stirred for 6 h. After the reaction was completed, the pH of the system was adjusted to neutral with 0.1 mol / L sodium bicarbonate aqueous solution, 100 ml of water was added, stirred, oscillated, and then left to stand, the organic phase was separated, the organic phase was rotary evaporated, and then silica gel column chromatography was performed with a mixture of petroleum ether and ethyl acetate as eluent, and then rotary evaporation was performed to obtain 11.02 g of compound 3. The mass spectrum M / Z (MS+H + ) of compound 3: 552.

[0026] Under a nitrogen atmosphere, 11.02 g of compound 3, 4.10 g of compound 4, 0.26 g of triphenylphosphine, 0.02 g of palladium-carbon, 4.04 g of triethylamine and 150 ml of toluene were added into the reaction system, heated to 120℃ and refluxed for 12 h; after the reaction was completed, the temperature was slightly lowered, and then diatomite was used for filtration; after the filtrate was cooled to room temperature, it was washed with water three times, then the organic phase was retained, and then the water phase was extracted with ethyl acetate; after the organic phases were combined, the organic phase was dried with anhydrous magnesium sulfate, filtered, rotary evaporated, and then silica gel column chromatography was performed with a mixture of petroleum ether and ethyl acetate as eluent, and then rotary evaporation was performed to obtain 8.44 g of antioxidant 1. The mass spectrum M / Z (MS+H + ) of antioxidant 1: 642, and the nuclear magnetic chart is shown in Figure 1 .

[0027] Synthesis Examples 2-5: Antioxidants 2-5 were sequentially prepared in synthesis examples 2-5, and the production method of synthesis example 1 was referred to, and compound 4 therein was replaced, and the rest was the same as synthesis example 1. The specific contents are shown in Table 1.

[0028] Table 1 Example 1: Preparation of low-color interference high-stability water-based marking ring environmental protection paint: 1. Raw material mass ratio: Base resin: 55 parts, epoxy acrylate resin, purchased from: Guangdong Fangxin Biotechnology Co., Ltd.; Wear-resistant filler: 35 parts, titanium white, purchased from: Shanghai Yuejiang Titanium White Chemical Product Co., Ltd.; Dispersant: 1 part, sodium diisooctyl succinate sulfonate, purchased from: Nantong Yixun Chemical Co., Ltd.; Defoaming agent: 0.3 parts, BYK-024, purchased from: Guangdong Wengjiang Chemical Reagent Co., Ltd.; Film-forming aid: 2 parts, alcohol ester twelve, purchased from: Shandong Xinheng Chemical Co., Ltd.; Thickening agent: 0.4 parts, Rongmenhas RM-8W, purchased from: Guangzhou Yaxinnovation Material Co., Ltd.; Antifreeze: 2 parts, ethylene glycol, purchased from: Jiangsu Runfeng Synthetic Technology Co., Ltd.; Antioxidant: 1 part, antioxidant 1; Deionized water: 15 parts.

[0029] 2. Production method: (1) Pre-dispersion stage: 15 parts of deionized water and 1 part of dispersant were added to a high-speed disperser and stirred at a speed of 400 r / min for 6 minutes until the dispersant was completely dissolved; 35 parts of wear-resistant filler was slowly added, and the temperature was raised to 28°C, then the speed was adjusted to 1300 r / min, and high-speed dispersion was carried out for 25 minutes. During the dispersion process, circulating water cooling was used to control the system temperature not to exceed 30°C, until the slurry fineness was ≤50 μm, to obtain a pre-dispersed slurry; (2) Resin mixing stage: the speed was reduced to 600 r / min, and 55 parts of base resin was slowly added, and continuous stirring was carried out for 15 minutes to ensure uniform mixing of the resin and the slurry; (3) Additive addition stage: keep the speed at 600 r / min, add 0.3 parts of defoaming agent, 2 parts of film-forming aid, 2 parts of antifreeze and 1 part of antioxidant 1 in turn, stir for 4 minutes after adding each additive, and continue to stir for 12 minutes after all the additives are added; (4) Viscosity adjustment and filtration stage: add 0.4 parts of thickening agent, stir at a speed of 600 r / min for 8 minutes, and finally filter with a 150 mesh nylon filter screen. After filtration, the paint was placed at 23°C for 15 minutes to remove residual micro-bubbles, and a low-color interference high-stability water-based marking environmental protection coating was obtained.

[0030] Examples 2-5: The preparation of low-color interference high-stability water-based marking environmental protection coating was carried out according to the production method of Example 1, and the antioxidant 1 therein was replaced by the antioxidants 2-5 prepared in Synthesis Examples 2-5 in turn, and the rest was the same as Example 1.

[0031] Comparative Example 1: Preparation of low color interference high stable waterborne marking environmentally friendly paint, referring to the production method of Example 1, replacing antioxidant 1 therein with antioxidant 1010, and the rest being the same as Example 1.

[0032] Comparative Example 2: Preparation of low color interference high stable waterborne marking environmentally friendly paint, referring to the production method of Example 1, replacing antioxidant 1 therein with antioxidant 300, and the rest being the same as Example 1.

[0033] Comparative Example 3: Preparation of low color interference high stable waterborne marking environmentally friendly paint, referring to the production method of Example 1, not adding antioxidant 1 therein, and the rest being the same as Example 1.

[0034] Comparative Example 4: Preparation of low color interference high stable waterborne marking environmentally friendly paint, referring to the production method of Example 1, not adding film forming aid therein, and the rest being the same as Example 1.

[0035] Comparative Example 5: Preparation of low color interference high stable waterborne marking environmentally friendly paint, referring to the production method of Example 1, not adding dispersant therein, and the rest being the same as Example 1.

[0036] Performance test: Sample preparation: The paint was coated on the asphalt substrate plate (size 150mm x 70mm x 5mm) according to the standard construction method (spraying), and cured for 3-5min under 340nm ultraviolet light, and then stored for 24h for standby, and the thickness after curing was 3mm.

[0037] 1. Adhesion test: According to GB / T 5210-2006 standard, the adhesion (MPa) of the coating was tested, and the results are shown in Table 2.

[0038] 2. Anti-aging test: According to GB / T 1865-2009 "Color paint and varnish Artificial climate aging and artificial radiation exposure (filtered xenon arc radiation)", the coating sample was tested by using a xenon lamp aging test box.

[0039] The test conditions were set as: blackboard temperature 63℃, relative humidity 50%, radiation intensity 0.71W / (m 2 ・340nm), water spraying cycle 18min / 102min, and continuous test for 2000h.

[0040] After the test, the color difference (ΔE) of the sample before and after the test was measured by a color difference meter, and the appearance of the coating was observed for phenomena such as powdering, cracking, peeling, etc.; the smaller the color difference and the appearance without obvious damage, the better the anti-aging property. The results are shown in Table 2.

[0041] According to GB / T 5210-2006 standard, the adhesion (MPa) between the coating and the substrate was tested, and the adhesion retention rate (%) after aging was calculated (adhesion before aging / adhesion after aging × 100%). The results are shown in Table 2.

[0042] Table 2.

[0043] Table 2 shows that the coatings of Examples 1-5 exhibit excellent performance in terms of adhesion, anti-aging properties, and adhesion retention rate after aging, with no obvious chalking, cracking, or peeling. In contrast, the coatings in the comparative examples, lacking key components (such as antioxidants or film-forming aids), showed a significant decrease in performance, poorer anti-aging properties, reduced adhesion retention rate, and varying degrees of chalking or cracking after aging. This demonstrates that the present invention, through optimized ingredient ratios and the addition of specific antioxidants, significantly improves the overall performance of the coatings, in stark contrast to the comparative examples.

[0044] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A low-color-interference, highly stable water-based environmentally friendly road marking paint, characterized in that: It is made from the following components in parts by weight: base resin: 40-60 parts, wear-resistant filler: 30-40 parts, dispersant: 0.5-1.5 parts, defoamer: 0.1-0.5 parts, film-forming aid: 1-3 parts, thickener: 0.1-0.5 parts, antifreeze: 1-3 parts, antioxidant: 0.5-2 parts, deionized water: 10-20 parts; The antioxidant is a compound represented by Formula 1: Formula 1: ; In Formula 1, R1 is a substituent, and R1 is selected from: methyl, amino, hydroxy, methoxy, and nitro.

2. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The base resin is one or more of epoxy acrylate resin, polyurethane acrylate resin, and polyester acrylate resin.

3. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The wear-resistant filler is one or more of titanium dioxide, silica powder, and glass microspheres.

4. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The dispersant is one or more of sodium diisooctyl succinate sulfonate or sodium dodecyl polyoxyethylene ether sulfate.

5. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The defoamer is one or more of BYK-024, BYK-028, and Tego-810.

6. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The film-forming aid is one or more of the following: dodecyl alcohol ester and dipropylene glycol butyl ether.

7. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The thickener is Rohm and Haas RM-8W; the antifreeze is ethylene glycol.

8. The low-color-interference, high-stability water-based environmentally friendly road marking coating according to claim 1, characterized in that, The antioxidant is any one of the following compounds: ； ； 。 9. A method for producing a low-color-interference, high-stability water-based environmentally friendly road marking paint according to any one of claims 1-8, characterized in that, Includes the following steps: (1) Pre-dispersion stage: Add the deionized water and dispersant to a high-speed disperser and stir at 300-500 r / min for 5-8 minutes until the dispersant is completely dissolved; then add the wear-resistant filler, heat to 25-30℃, adjust the speed to 1000-1500 r / min and disperse at high speed for 15-30 minutes until the fineness of the system is ≤50μm to obtain the pre-dispersion slurry; (2) Resin mixing stage: Reduce the speed of the high-speed disperser to 500-800 r / min, add the base resin to the pre-dispersed slurry, and continue stirring for 10-20 minutes to ensure that the resin and slurry are mixed evenly; (3) Additive addition stage: Keep the speed at 500-800r / min and add the defoamer, film-forming aid, antifreeze and antioxidant in sequence. Stir for 3-5 minutes after each additive is added. After all additives are added, continue stirring for 8-15 minutes. (4) Thickening and filtration stage: Add the thickener and stir at 500-800 r / min for 5-10 minutes; finally, filter with a 100-200 mesh filter to remove undispersed particles and impurities, and obtain a low-color-interference, high-stability water-based environmentally friendly road marking paint.

10. The production method of the low-color-interference, high-stability water-based road marking environmentally friendly coating according to claim 9, characterized in that, In step (1), circulating water cooling is used during the high-speed dispersion process to maintain the system temperature at no more than 30°C; In step (4), a 150-mesh nylon filter is used for filtration. After filtration, the coating is left to stand at 20-25℃ for 10-20 minutes to remove residual microbubbles in the system.

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