A paint composition for pavement marking and a method for preparing the same

Abstract

The application discloses a paint composition for road surface marking and a preparation method thereof, and belongs to the technical field of paint production, and is used for solving the technical problem that the fluorescent performance and wear resistance of the road surface paint in the prior art need to be further improved; the application comprises the following raw material components in parts by weight: 40-60 parts of whitening polyacrylic acid resin, 20-30 parts of functionalized filler and 6-12 parts of auxiliary materials; the phosphor is surface-modified to enhance the water resistance and compatibility with organic materials, the phosphor is used as a crosslinking agent to react with the whitening polyacrylate, the high-reflection performance of the whitening polyacrylate is synergistically matched to enhance the warning effect at night, the surface of the functionalized filler is modified with a transparent material to enhance the penetration performance of ultraviolet rays in the material, the absorption performance of the phosphor and ultraviolet ray initiators to ultraviolet rays is improved, and finally the paint composition is prepared.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of paint production, in particular to a paint composition for road marking and a preparation method thereof. BACKGROUND

[0002] The paint for road marking has undergone significant technical evolution since its early application, with the main purpose being to improve its performance in terms of fluorescence and durability. Initially, asphalt-based or oil-based paints were used for road marking, which were easy to apply but had poor visibility at night or in adverse weather conditions. To improve this situation, research teams introduced tiny glass beads that could reflect vehicle light, significantly improving visibility at night. Recently, the application of nanotechnology and environmentally friendly materials represents the latest development direction of road marking paint technology. These materials not only improve the fluorescence properties and durability of the coating, but also help reduce environmental burden. This series of technological progress continuously improves the functionality of road marking, ensuring driving safety and road use efficiency.

[0003] The prior art CN117887316B discloses an anti-skid road marking paint and its preparation method, belonging to the technical field of paint preparation, comprising the following components by weight: photocuring resin 40-50 parts, night light hollow glass microspheres 5-10 parts, elastic filler I 15-20 parts, elastic filler II 15-20 parts, pigment 0.1-2 parts, and photoinitiator 1-5 parts. The preparation method is as follows: mix silane coupling agent, ethanol, and night light powder, stir uniformly, and spray on the surface of etched hollow glass microspheres to obtain night light hollow glass microspheres. Mix the photoinitiator with the photocuring resin uniformly, and then add the night light hollow glass microspheres, elastic filler I, elastic filler II, and pigment into the photocuring resin system in sequence to obtain the road marking paint. The above patent content adds night light hollow glass microspheres, elastic filler I, and elastic filler II to the road marking paint to solve the problems of insufficient visibility and poor anti-skid performance of the road marking paint in adverse weather and dark light environments.

[0004] However, the above patent content grafts night light powder on the surface of the etched glass microsphere crystal type to endow the glass microsphere surface with fluorescence properties, thereby overcoming the problem of insufficient visibility of the road marking paint in adverse weather and dark light environments. However, the night light powder selected in the above patent content is an aluminate long-afterglow luminescent material, which has poor water resistance, leading to easy decline of the fluorescence performance of the paint laid on outdoor roads. The aluminate after hydrolysis is prone to structural transformation, thereby damaging the paint structure and further leading to the need for further improvement of the wear resistance of the material.

[0005] In view of the above technical defects, a solution is proposed. SUMMARY

[0006] The present application aims to provide a paint composition for road surface marking and a preparation method thereof, to solve the technical problem that the fluorescent performance and wear resistance of the road surface paint in the prior art need to be further improved.

[0007] The present application can be achieved by the following technical solutions.

[0008] The paint composition for road surface marking comprises the following raw material components in parts by weight: 40-60 parts of whitening polyacrylic acid resin, 20-30 parts of functionalized filler, and 6-12 parts of auxiliary materials.

[0009] The preparation method of the functionalized filler comprises the following steps.

[0010] A1, the self-repairing filler, methyl-4-cyclooctene-1-yl carbonate, triethylamine and N,N-dimethylformamide are added into a reaction kettle, the temperature of the reaction kettle is raised to 60-80 DEG C, and the reaction is kept for 40-60 min, and the functionalized filler precursor is obtained after post-treatment;

[0011] The reaction principle for preparing the functionalized filler precursor is that, under the catalysis of alkaline conditions and heating conditions, the ring-opening reaction of the epoxy groups on the surface of the self-repairing filler produces free radicals, and the free radicals react with the carboxyl groups on the methyl-4-cyclooctene-1-yl carbonate, so that the methyl-4-cyclooctene-1-yl carbonate is uniformly dispersed on the surface of the self-repairing filler, and finally the functionalized filler precursor is prepared.

[0012] A2, the functionalized filler precursor and N,N-dimethylformamide are added into an ultrasonic instrument, the frequency of the ultrasonic instrument is set to 10-20 kHz, the temperature is raised to 60-80 DEG C, then azobisisobutyronitrile is added into the ultrasonic instrument, the reaction is kept for 1-2 h, and the functionalized filler is obtained after post-treatment.

[0013] The reaction principle for preparing the functionalized filler is that, there are a large number of double bond structures introduced by the vinyltrimethoxysilane on the surface of the functionalized filler precursor, and the double bonds on the methyl-4-cyclooctene-1-yl carbonate on the surface of the functionalized filler precursor produce free radicals under the catalysis of the free radical initiator and heating conditions, and a modified layer with a large number of carbonate is formed on the surface of the functionalized filler precursor through continuous polymerization, and the functionalized filler is obtained.

[0014] Further, in step A1, the amount ratio of the self-repairing filler, methyl-4-cyclooctene-1-yl carbonate, triethylamine and N,N-dimethylformamide is 8-10 g:4-5 g:2-3 g:60-70 mL, and the post-treatment comprises: after the reaction is completed, the reaction liquid is suction filtered, the filter cake is collected, the filter cake is washed with anhydrous ethanol and deionized water for 3-5 times, then the filter cake is placed in a drying box with a temperature of 60 DEG C for vacuum drying to obtain the functionalized filler precursor.

[0015] Further, in step A2, the ratio of the amounts of the functionalized filler precursor, N,N-dimethylformamide and azobisisobutyronitrile is 4-5 g: 15-20 mL: 0.1-0.2 g, and the post-treatment includes: after the reaction is completed, the reaction solution is suction filtered, the filter cake is collected, and the filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then the filter cake is placed in a drying oven at a temperature of 60°C for vacuum drying to obtain the functionalized filler.

[0016] Further, the auxiliary material includes the following raw material components in parts by weight: 3-5 parts of titanium white, 1-2 parts of a leveling agent, 1-2 parts of a dispersing agent, and 1-3 parts of an ultraviolet light absorber; the leveling agent is one or more of dimethyl silicone oil, ethoxylated silicone oil, and polyether-modified silicone oil; the dispersing agent is one or more of sodium polycarboxylate, ammonium polyphosphate, and hydroxyethyl cellulose; and the ultraviolet light absorber is one or more of 2,4-dihydroxyphenone, 2,4,6-tris[(2'-hydroxy-5'-methylphenyl)methyl]-1,3,5-triazine, and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole.

[0017] Further, the method for preparing the self-repairing filler includes the following steps:

[0018] B1, allyl methyl carbonate, triphenyloxy vinyl silane, 4,4'-dimethoxybenzophenone and methyl orthosilicate are added to a reaction kettle and stirred for 5-10 min to obtain an oil phase solution;

[0019] B2, the oil phase solution is added to an ultrasonic emulsifier, and sorbitan oleate and deionized water are poured into the ultrasonic emulsifier, the frequency of the ultrasonic emulsifier is set to 20-40 kHz, and ultrasonic treatment is performed at room temperature for 20-30 min to obtain a mixed emulsion;

[0020] B3, the mixed emulsion is added to the reaction kettle and stirred, saturated sodium hydroxide solution is added dropwise to the reaction kettle to adjust the pH of the system to 8-10, the temperature of the reaction kettle is increased to 40-50°C, and after being kept at this temperature for 2-3 h, the temperature of the reaction kettle is reduced to 0-5°C, and a modifier is added in two equal portions, and after the two additions, each portion is kept for 1-2 h, and the self-repairing filler is obtained after post-treatment.

[0021] The reaction principle for preparing the self-repairing filler is as follows: after deionized water and a surfactant are poured into the oil phase solution and stirred at high speed, an oil-in-water structure is formed, after the pH of the system is adjusted, the methyl orthosilicate in the oil phase solution is hydrolyzed at the water-oil interface and finally hydrolyzed on the surface of the oil phase droplets to form a stable crosslinked structure, and after the addition of a modifier, a stable and dense structure and a modified functional group are further formed on the surface of the capsule, and finally the self-repairing filler is prepared.

[0022] Further, in step B1, the ratio of allyl methyl carbonate, triphenyloxy vinyl silane, 4,4'-dimethoxybenzophenone and methyl orthosilicate is 5-8 g:3-5 g:0.3-0.5 g:20-30 mL; in step B2, the ratio of the oil phase solution, sorbitan oleate and deionized water is 10-12 mL:3-4 mL:40-60 mL.

[0023] In step B3, the ratio of the mixed emulsion and the modifier is 40 mL:3-5 mL, the modifier is a mixture of vinyl trimethoxysilane and 3-(2,3-epoxypropoxy) propyl trimethoxysilane in a volume ratio of 1 mL:1-1.5 mL, and the post-treatment includes: after the reaction is completed, the reaction solution is suction filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 3-5 times, and then the filter cake is placed in a drying box at a temperature of 60°C and vacuum dried until the filter cake reaches a constant weight, to obtain the self-repairing filler.

[0024] Further, the preparation method of the whitening polyacrylic acid resin is as follows: acrylic acid, 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 1-allyloxy-2,3-epoxypropane, azobisisobutyronitrile and dimethyl sulfoxide are added to a reaction kettle and stirred, the temperature of the reaction kettle is increased to 60-80°C, and after being kept at the temperature and stirred for 1-2 h, the afterglow crosslinking agent and benzoic acid are added to the reaction kettle, and kept at temperature for 20-30 min, and the post-treatment is performed to obtain the whitening polyacrylic acid resin.

[0025] The reaction equation for preparing the whitening polyacrylic acid resin is as follows:

[0026]

[0027] In the formula, “ ” represents an active crosslinking site of the organic chain segment.

[0028] The reaction principle for preparing the whitening polyacrylic acid resin is as follows: under the catalysis of the free radical initiator and heating, the double bonds on the acrylic acid, 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene and 1-allyloxy-2,3-epoxypropane undergo free radical addition reaction, and long-chain polyacrylic chain segments are prepared by continuous polymerization of the double bonds; and under the catalysis of benzoic acid, the epoxy group on the chain segment undergoes ring opening reaction with the hydroxyl group on the afterglow crosslinking agent, to finally prepare the whitening polyacrylic acid resin.

[0029] ​Further, the stirring rate of the reaction kettle is 80-120 rpm, and the amount ratio of acrylic acid, 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 1-allyloxy-2,3-epoxypropane, azobisisobutyronitrile, dimethyl sulfoxide, afterglow crosslinking agent and benzoic acid is 8-10 g:2-3 g:4-5 g:0.3-0.5 g:45-60 mL:2-3 g:0.8-1 g, and the post-treatment includes: after the reaction is completed, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100 ℃, and vacuum distillation is performed until no liquid is produced, to obtain the whitening polyacrylic acid resin

[0030] Further, the preparation method of the afterglow crosslinking agent includes the following steps:

[0031] C1, 3-(methacryloyloxy) propyl trimethoxysilane and anhydrous ethanol are added into a reaction kettle, and strontium aluminate is added after stirring at room temperature for 15 min, the reaction kettle is sealed, and heating is performed at a temperature water bath of 50-60 ℃ for 2-4 h, and the post-treatment obtains modified strontium aluminate;

[0032] The reaction principle for preparing the modified strontium aluminate is that, under hydrothermal conditions, the siloxane chain segment on the 3-(methacryloyloxy) propyl trimethoxysilane is hydrolyzed to form a silanol structure, crosslinking occurs with the hydroxyl group on the strontium aluminate, a coating layer is finally formed on the surface of the aluminate, and the modified strontium aluminate is obtained.

[0033] C2, the modified strontium aluminate is placed in a reaction kettle containing an acrylic acid(hydroxymethyl) ester / ethylene glycol solution, the temperature of the reaction kettle is increased to 60-80 ℃, and potassium persulfate is added dropwise while stirring, until flocculent precipitate is produced, and the post-treatment obtains the afterglow crosslinking agent.

[0034] The reaction principle for preparing the afterglow crosslinking agent is that, under the catalysis of a free radical initiator and heating, the double bond on the surface of the modified strontium aluminate reacts, a poly(acrylic acid(hydroxymethyl) ester coating layer is finally formed on the surface of the modified strontium aluminate, and when the precipitate appears, it indicates that there is poly(acrylic acid(hydroxymethyl) ester self-polymerization in the reaction, which reduces the dispersibility of the material, so the reaction process is ended, and the post-treatment obtains the afterglow crosslinking agent.

[0035] Further, in step C1, the stirring rate of the reaction kettle is 80-120 rpm, and the amount ratio of 3-(methacryloyloxy) propyl trimethoxysilane, anhydrous ethanol and strontium aluminate is 4-5 g:40-60 mL:20-30 g, and the post-treatment includes: after the reaction is completed, the reaction liquid is filtered, the filter cake is collected, the filter cake is washed with anhydrous ethanol for 3-5 times, and then the filter cake is placed in a drying box with a temperature of 60 ℃ for vacuum drying until the filter cake reaches a constant weight, to obtain the modified strontium aluminate.

[0036] Further, in step C2, the amount ratio of modified strontium aluminate, (hydroxymethyl) acrylate / ethylene glycol solution and potassium persulfate is 4-5g:20-25mL:0.3-0.5g, the (hydroxymethyl) acrylate / ethylene glycol solution is obtained by mixing (hydroxymethyl) acrylate and ethylene glycol in an amount ratio of 1mL:3-5mL, and the post-treatment includes: after the reaction is completed, the reaction solution is suction filtered, the filter cake is collected, and the filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then the filter cake is placed in a drying box at a temperature of 60 DEG C and vacuum dried until the filter cake reaches a constant weight, to obtain the afterglow crosslinking agent.

[0037] The application also provides a preparation method of the paint composition for road surface marking, including the following steps: adding whitening polyacrylic acid resin, functionalized repair filler, titanium white, leveling agent, dispersant and ultraviolet absorber into a reaction kettle, mixing uniformly, and passing through a 300-500 mesh screen to obtain the paint composition.

[0038] The application has the following advantages:

[0039] 1、The application enhances the water resistance and compatibility with organic materials of the phosphor by surface modification, the poly(hydroxymethyl) acrylate on the surface of the phosphor enhances the crosslinking of the whitening polyacrylate as a crosslinking agent, the whitening polyacrylate also provides protection for the stability of the phosphor, enhances the wear resistance of the material, overcomes the poor water resistance of strontium aluminate, thereby improving the water resistance of the material, and the dispersion performance of strontium aluminate in the paint system is significantly improved after organic modification, thereby improving the stop excitation brightness of the material, ensuring the warning effect of the material at night, enhancing the warning effect at night through the high light reflection performance of the whitening polyacrylate, and enhancing the penetration performance of ultraviolet rays in the material through the surface modification of transparent materials on the functionalized filler, thereby improving the absorption performance of the phosphor and ultraviolet initiator to ultraviolet rays, and finally preparing the paint composition.

[0040] 2、The application modifies the epoxy group on the surface of the self-repairing filler, which is crosslinked with the carboxyl group on the methyl-4-cyclooctene-1-yl carbonate, so that the carbonate is uniformly dispersed on the surface of the self-repairing filler, and then the stable coating structure is formed through self-polymerization and polymerization of the double bond on the surface of the self-repairing filler, compared with direct solution polymerization, the self-polymerization reaction of methyl-4-cyclooctene-1-yl carbonate is inhibited, thereby significantly improving the dispersion capacity of the functionalized filler, and the transparent polycarbonate component is dispersed in the paint, which greatly improves the absorption capacity of strontium aluminate to ultraviolet rays, thereby enhancing the brightness of 60min stop excitation, when the coating is damaged, the functionalized filler inside is broken, the photoinitiator inside the functionalized filler is activated, the repair monomer inside the functionalized filler promotes the repair of the gap on the surface of the coating, enhances the wear resistance of the material, promotes the self-polymerization repair process of the coated product, and ensures the improvement of the fluorescent performance of the coated product.

[0041] 3、The prepared whitening polyacrylate organic segment is internally modified by epoxy groups and fluorescent whitening groups, the epoxy groups improve the flowability and wetting behavior of the coating on the substrate, help to form a more uniform and tight coating layer, thereby improving the adhesion, and the three-membered ring structure of the epoxy groups has high reactivity in ring-opening reaction, when the epoxy groups contact with the functional groups on the surface of the substrate, chemical reaction can occur through the formation of covalent bond, thereby greatly improving the adhesion strength of the coating; the electrons of the fluorescent whitening groups are excited to a higher energy level, and then when the electrons fall to a low energy level, energy is released in the form of long-wavelength light, after the release of blue light, the yellow or dark tone of the material itself is compensated, so that the material looks brighter and whiter, and in a lower light environment, the material appears brighter, improving its overall visual appeal and ensuring the eye-catching effect of the coating during the day and the warning effect at night. DETAILED DESCRIPTION

[0042] The technical solutions of the present application will be described below in conjunction with the embodiments, obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0043] Embodiment 1

[0044] The present embodiment provides a preparation method of a residual fluorescence crosslinking agent for a pavement marking coating composition, comprising the following steps:

[0045] Step 1, preparation of modified strontium aluminate

[0046] 400.0g 3-(methacryloyloxy)propyl trimethoxysilane and 4.0L anhydrous ethanol were added to the reaction kettle, stirred at room temperature for 15min, then 2.0kg strontium aluminate was added, the stirring rate was 80rpm, the reaction kettle was sealed, heated in a water bath at 50℃ for 2h, after the reaction was completed, the reaction liquid was filtered, the filter cake was collected, washed with anhydrous ethanol for 3 times, then the filter cake was placed in a drying box at a temperature of 60℃ and vacuum dried to constant weight, to obtain modified strontium aluminate.

[0047] Step 2, residual fluorescence crosslinking agent

[0048] Weigh: 100.0mL of (hydroxymethyl) acrylate and 300.0mL of ethylene glycol to obtain a (hydroxymethyl) acrylate / ethylene glycol solution;

[0049] Weighing: 400.0g of modified strontium aluminate is placed in a reaction kettle containing 2.0L of a (hydroxymethyl) acrylate / ethylene glycol solution, the temperature of the reaction kettle is raised to 60°C, and 30.0g of potassium persulfate is added dropwise while stirring, until a flocculent precipitate is produced, after the reaction is complete, the reaction solution is filtered, the filter cake is collected, washed 3 times with anhydrous ethanol and deionized water, and then placed in a drying oven at a temperature of 60°C and vacuum dried to a constant weight of the filter cake, to obtain a residual glow crosslinking agent.

[0050] Example 2

[0051] The present embodiment provides a preparation method of a residual glow crosslinking agent for a pavement marking paint composition, comprising the following steps:

[0052] Step 1, preparation of modified strontium aluminate

[0053] 500.0g of 3-(methacryloyloxy)propyl trimethoxysilane and 6.0L of anhydrous ethanol are added to a reaction kettle, stirred at room temperature for 15min, then 3.0kg of strontium aluminate is added, the stirring rate is 120rpm, the reaction kettle is sealed and heated in a water bath at 60°C for 4h, after the reaction is complete, the reaction solution is filtered, the filter cake is collected, washed 5 times with anhydrous ethanol, and then placed in a drying oven at a temperature of 60°C and vacuum dried to a constant weight of the filter cake, to obtain modified strontium aluminate.

[0054] Step 2, residual glow crosslinking agent

[0055] Weighing: 100.0mL of (hydroxymethyl) acrylate and 500.0mL of ethylene glycol are mixed to obtain a (hydroxymethyl) acrylate / ethylene glycol solution;

[0056] Weighing: 500.0g of modified strontium aluminate is placed in a reaction kettle containing 2.5L of a (hydroxymethyl) acrylate / ethylene glycol solution, the temperature of the reaction kettle is raised to 80°C, and 50.0g of potassium persulfate is added dropwise while stirring, until a flocculent precipitate is produced, after the reaction is complete, the reaction solution is filtered, the filter cake is collected, washed 5 times with anhydrous ethanol and deionized water, and then placed in a drying oven at a temperature of 60°C and vacuum dried to a constant weight of the filter cake, to obtain a residual glow crosslinking agent.

[0057] Example 3

[0058] The present embodiment provides a preparation method of a residual glow crosslinking agent for a pavement marking paint composition, comprising the following steps:

[0059] Step 1, preparation of modified strontium aluminate

[0060] Into a reaction kettle, 450.0 g of 3-(methacryloyloxy)propyl trimethoxysilane and 5.0 L of anhydrous ethanol were added, stirred at room temperature for 15 min, then 2.5 kg of strontium aluminate was added, the stirring rate was 100 rpm, the reaction kettle was sealed, heated in a 55℃ temperature water bath for 3 h, after the reaction was completed, the reaction solution was filtered, the filter cake was collected, washed with anhydrous ethanol 4 times, then the filter cake was placed in a drying oven at a temperature of 60℃ and vacuum dried to a constant weight of the filter cake, to obtain the modified strontium aluminate.

[0061] Step 2, afterglow crosslinking agent

[0062] Weighing: 100.0 mL of (hydroxymethyl) acrylate and 400.0 mL of ethylene glycol were mixed to obtain a (hydroxymethyl) acrylate / ethylene glycol solution;

[0063] Weighing: 450.0 g of modified strontium aluminate was placed in a reaction kettle containing 2.1 L of (hydroxymethyl) acrylate / ethylene glycol solution, the temperature of the reaction kettle was raised to 70℃, while stirring, 40.0 g of potassium persulfate was added dropwise until a flocculent precipitate was produced, after the reaction was completed, the reaction solution was filtered, the filter cake was collected, washed with anhydrous ethanol and deionized water 4 times, then the filter cake was placed in a drying oven at a temperature of 60℃ and vacuum dried to a constant weight of the filter cake, to obtain the afterglow crosslinking agent.

[0064] Example 4

[0065] The present embodiment provides a functional filler for a pavement marking paint composition, a preparation method of a self-repairing filler, comprising the following steps:

[0066] Step 1, preparation of oil phase solution

[0067] Weighing: 500.0 g of allyl methyl carbonate, 300.0 g of triphenyloxy vinyl silane, 30.0 g of 4,4'-dimethoxybenzophenone and 2.0 L of methyl orthosilicate were added to a reaction kettle and stirred, stirred for 5 min to obtain an oil phase solution.

[0068] Step 2, preparation of mixed emulsion

[0069] Weighing: 1.0 L of oil phase solution was added to an ultrasonic emulsifier, and 300.0 mL of sorbitan oleate and 4.0 L of deionized water were poured into the ultrasonic emulsifier, the frequency of the ultrasonic emulsifier was set to 20 kHz, and ultrasonic was applied at room temperature for 20 min to obtain a mixed emulsion.

[0070] Step 3, preparation of self-repairing filler

[0071] Weighing: 100.0 mL of vinyl trimethoxysilane and 100.0 mL of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were mixed to obtain a modifier;

[0072] Weighing: 4.0L of the mixed emulsion was added to the reaction kettle for stirring, saturated sodium hydroxide solution was added dropwise to the reaction kettle to adjust the system pH = 8, the temperature of the reaction kettle was raised to 40℃, and after 2h of insulation, the temperature of the reaction kettle was reduced to 5℃, 300.0mL of modifier was added in two equal amounts, both after two additions were insulated for 1h, after the reaction was completed, the reaction liquid was filtered, the filter cake was collected, washed with anhydrous ethanol and deionized water for 3 times, and then the filter cake was placed in a drying oven at a temperature of 60℃ for vacuum drying until the filter cake reached a constant weight, to obtain the self-repairing filler.

[0073] Example 5

[0074] The present embodiment provides a functionalized filler for a pavement marking paint composition, a preparation method of a self-repairing filler, comprising the following steps:

[0075] Step ①, preparation of oil phase solution

[0076] Weighing: 800.0g of allyl methyl carbonate, 500.0g of triphenyloxy vinyl silane, 50.0g of 4,4'-dimethoxybenzophenone and 3.0L of methyl orthosilicate were added to the reaction kettle for stirring, and stirring for 10min to obtain the oil phase solution.

[0077] Step ②, preparation of mixed emulsion

[0078] Weighing: 1.2L of the oil phase solution was added to the ultrasonic emulsifier, and 400.0mL of sorbitan oleate and 6.0L of deionized water were poured into the ultrasonic emulsifier, the frequency of the ultrasonic emulsifier was set to 40kHz, and ultrasonic was performed at room temperature for 30min to obtain the mixed emulsion.

[0079] Step ③, preparation of self-repairing filler

[0080] Weighing: 100.0mL of vinyl trimethoxysilane and 150.0mL of 3-(2,3-epoxypropoxy) propyl trimethoxysilane were mixed to obtain the modifier;

[0081] Weighing: 4.0L of the mixed emulsion was added to the reaction kettle for stirring, saturated sodium hydroxide solution was added dropwise to the reaction kettle to adjust the system pH = 10, the temperature of the reaction kettle was raised to 50℃, and after 3h of insulation, the temperature of the reaction kettle was reduced to 0℃, 500.0mL of modifier was added in two equal amounts, both after two additions were insulated for 2h, after the reaction was completed, the reaction liquid was filtered, the filter cake was collected, washed with anhydrous ethanol and deionized water for 5 times, and then the filter cake was placed in a drying oven at a temperature of 60℃ for vacuum drying until the filter cake reached a constant weight, to obtain the self-repairing filler.

[0082] Example 6

[0083] The embodiment provides a functional filler for a pavement marking paint composition, a preparation method of the self-repairing filler, and the method comprises the following steps.

[0084] Step 1, preparing an oil phase solution

[0085] Take 600.0 g of allyl methyl carbonate, 350.0 g of triphenyloxy vinyl silane, 40.0 g of 4,4'-dimethoxybenzophenone and 2.5 L of methyl orthosilicate into a reaction kettle, stir, and stir for 8 min to obtain an oil phase solution.

[0086] Step 2, preparing a mixed emulsion

[0087] Take 1.0 L of the oil phase solution into an ultrasonic emulsifier, pour 350.0 mL of sorbitan oleate and 5.0 L of deionized water into the ultrasonic emulsifier, set the frequency of the ultrasonic emulsifier to 30 kHz, and ultrasonically emulsify at room temperature for 25 min to obtain a mixed emulsion.

[0088] Step 3, preparing a self-repairing filler

[0089] Take 100.0 mL of vinyl trimethoxysilane and 120.0 mL of 3-(2,3-epoxypropoxy) propyl trimethoxysilane to mix a modifier;

[0090] Take 4.0 L of the mixed emulsion into a reaction kettle, stir, add saturated sodium hydroxide solution dropwise into the reaction kettle to adjust the pH value of the system to 9, increase the temperature of the reaction kettle to 45 DEG C, keep the temperature for 2 h, then decrease the temperature of the reaction kettle to 3 DEG C, add 400.0 mL of the modifier in two equal portions, keep the temperature for 2 h after each addition, after the reaction is completed, filter the reaction solution, collect the filter cake, wash the filter cake with anhydrous ethanol and deionized water for 4 times, then place the filter cake in a drying box with a temperature of 60 DEG C to vacuum dry until the weight of the filter cake is constant to obtain a self-repairing filler.

[0091] Example 7

[0092] The embodiment provides a preparation method of a functional filler for a pavement marking paint composition, and the method comprises the following steps.

[0093] Step I, preparing a functional filler precursor

[0094] Take 800.0 g of the self-repairing filler prepared in Example 4, 400.0 g of methyl-4-cyclooctene-1-yl carbonate, 200.0 g of triethylamine and 6.0 L of N,N-dimethylformamide into a reaction kettle, increase the temperature of the reaction kettle to 60 DEG C, keep the temperature for 40 min, after the reaction is completed, filter the reaction solution, collect the filter cake, wash the filter cake with anhydrous ethanol and deionized water for 3 times, and then place the filter cake in a drying box with a temperature of 60 DEG C to vacuum dry to obtain a functional filler precursor.

[0095] Step II, preparation of functionalized filler

[0096] Weighing: 400.0 g of functionalized filler precursor and 1.5 L of N,N- dimethylformamide into the ultrasonic instrument, the frequency of the ultrasonic instrument is set to 10 kHz, after the temperature is raised to 60℃, 10.0 g of azobisisobutyronitrile is added into the ultrasonic instrument, and the reaction is kept for 1 h. After the reaction is completed, the reaction solution is filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 3 times, and then the filter cake is placed in a drying box with a temperature of 60℃ for vacuum drying to obtain the functionalized filler.

[0097] Example 8

[0098] The present example provides a preparation method of functionalized filler for pavement marking paint composition, comprising the following steps:

[0099] Step I, preparation of functionalized filler precursor

[0100] Weighing: 1000.0 g of self-repairing filler prepared in Example 5, 500.0 g of methyl-4-cycloocten-1-yl carbonate, 300.0 g of triethylamine and 7.0 L of N,N- dimethylformamide into the reaction kettle, the temperature of the reaction kettle is raised to 80℃, and the reaction is kept for 60 min. After the reaction is completed, the reaction solution is filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 5 times, and then the filter cake is placed in a drying box with a temperature of 60℃ for vacuum drying to obtain the functionalized filler precursor.

[0101] Step II, preparation of functionalized filler

[0102] Weighing: 500.0 g of functionalized filler precursor and 2.0 L of N,N- dimethylformamide into the ultrasonic instrument, the frequency of the ultrasonic instrument is set to 20 kHz, after the temperature is raised to 80℃, 20.0 g of azobisisobutyronitrile is added into the ultrasonic instrument, and the reaction is kept for 2 h. After the reaction is completed, the reaction solution is filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 5 times, and then the filter cake is placed in a drying box with a temperature of 60℃ for vacuum drying to obtain the functionalized filler.

[0103] Example 9

[0104] The present example provides a preparation method of functionalized filler for pavement marking paint composition, comprising the following steps:

[0105] Step I, preparation of functionalized filler precursor

[0106] Weighing: 900.0 g of the self-repairing filler prepared in Example 6, 500.0 g of methyl-4-cycloocten-1-yl carbonate, 250.0 g of triethylamine and 6.5 L of N,N-dimethylformamide into a reaction kettle, the temperature of the reaction kettle is raised to 70 ℃, and the reaction is kept for 50 min. After the reaction is completed, the reaction solution is filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 4 times, and then the filter cake is placed in a drying box at a temperature of 60 ℃ for vacuum drying to obtain a functional filler precursor.

[0107] Step II, preparation of functional filler

[0108] Weighing: 450.0 g of the functional filler precursor and 1.8 L of N,N-dimethylformamide into an ultrasonic instrument, the frequency of the ultrasonic instrument is set to 15 kHz, the temperature is raised to 70 ℃, then 15.0 g of azobisisobutyronitrile is added into the ultrasonic instrument, and the reaction is kept for 1 h. After the reaction is completed, the reaction solution is filtered, the filter cake is collected, washed with anhydrous ethanol and deionized water for 4 times, and then the filter cake is placed in a drying box at a temperature of 60 ℃ for vacuum drying to obtain a functional filler.

[0109] Example 10

[0110] The present embodiment provides a preparation method of a coating composition for road marking, comprising the following steps:

[0111] Step I, preparation of whitening polyacrylic acid resin

[0112] Weighing: 800.0 g of acrylic acid, 200.0 g of 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 400.0 g of 1-allyloxy-2,3-epoxypropane, 30.0 g of azobisisobutyronitrile and 4.5 L of dimethyl sulfoxide into a reaction kettle and stir, the temperature of the reaction kettle is raised to 60 ℃, and the stirring is kept for 4 h. Then 200.0 g of the afterglow crosslinking agent prepared in Example 1 and 80.0 g of benzoic acid are added into the reaction kettle, and the reaction is kept for 20 min. After the reaction is completed, the reaction kettle is cooled to room temperature, then the reaction solution is added into a rotary evaporator with a water bath temperature of 80 ℃, and distilled under reduced pressure until no liquid is collected to obtain a whitening polyacrylic acid resin.

[0113] Step II, preparation of whitening polyacrylic acid resin

[0114] Weighing: 4.0 kg of the whitening polyacrylic acid resin, 2.0 kg of the functional filler prepared in Example 7, 300.0 g of titanium white, 100.0 g of ethoxylated silicone oil, 100.0 g of sodium polycarboxylate and 100.0 g of 2,4-dihydroxyphenone into a reaction kettle and mix uniformly, pass through a 500 mesh screen to obtain a coating composition.

[0115] Example 11

[0116] The embodiment provides a preparation method of a paint composition for road surface marking, and comprises the following steps:

[0117] Step one, preparation of whitening polyacrylic acid resin

[0118] Take 1000.0 g of acrylic acid, 300.0 g of 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 500.0 g of 1-allyloxy-2,3-epoxypropane, 50.0 g of azobisdimethyl isobutyronitrile and 6.0 L of dimethyl sulfoxide into a reaction kettle and stir, the stirring rate is 120 rpm, the temperature of the reaction kettle is increased to 80 DEG C, after 2 h of heat preservation and stirring, 300.0 g of the afterglow crosslinking agent prepared in example 2 and 100.0 g of benzoic acid are added into the reaction kettle, heat preservation and reaction are conducted for 30 min, after the reaction is completed, the reaction kettle is cooled to room temperature, then the reaction solution is added into a rotary evaporator with a water bath temperature of 100 DEG C, and vacuum distillation is conducted until no liquid is collected, thereby obtaining the whitening polyacrylic acid resin.

[0119] Step two, preparation of whitening polyacrylic acid resin

[0120] Take 6.0 kg of the whitening polyacrylic acid resin, 3.0 kg of the functionalized filler prepared in example 8, 500.0 g of titanium white, 200.0 g of ethoxylated silicone oil, 200.0 g of sodium polycarboxylate and 300.0 g of 2,4-dihydroxyphenone into a reaction kettle and mix uniformly, pass through a 500-mesh screen, and thereby obtain the paint composition.

[0121] Example 12

[0122] The embodiment provides a preparation method of a paint composition for road surface marking, and comprises the following steps:

[0123] Step one, preparation of whitening polyacrylic acid resin

[0124] Take 900.0 g of acrylic acid, 250.0 g of 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 450.0 g of 1-allyloxy-2,3-epoxypropane, 40.0 g of azobisdimethyl isobutyronitrile and 5.4 L of dimethyl sulfoxide into a reaction kettle and stir, the stirring rate is 100 rpm, the temperature of the reaction kettle is increased to 70 DEG C, after 1 h of heat preservation and stirring, 250.0 g of the afterglow crosslinking agent prepared in example 3 and 90.0 g of benzoic acid are added into the reaction kettle, heat preservation and reaction are conducted for 24 min, after the reaction is completed, the reaction kettle is cooled to room temperature, then the reaction solution is added into a rotary evaporator with a water bath temperature of 90 DEG C, and vacuum distillation is conducted until no liquid is collected, thereby obtaining the whitening polyacrylic acid resin.

[0125] Step two, preparation of whitening polyacrylic acid resin

[0126] Take: 5.0 kg of whitening polypropylene acid resin, 2.5 kg of functional filler prepared in Example 9, 400.0 g of titanium white, 150.0 g of ethoxylated silicone oil, 150.0 g of sodium polycarboxylate and 200.0 g of 2,4-dihydroxyacetophenone into the reaction kettle and mix well, pass through a 400 mesh screen to obtain a coating composition.

[0127] Comparative Example 1

[0128] The difference between this comparative example and Example 12 is that the residual crosslinking agent used in the preparation process cancels step 2.

[0129] Comparative Example 2

[0130] The difference between this comparative example and Example 12 is that the self-healing filler prepared in Example 6 is used instead of the functional filler in step one.

[0131] Comparative Example 3

[0132] The difference between this comparative example and Example 12 is that in step one, acrylic acid is used instead of 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene and 1-allyloxy-2,3-epoxy propane.

[0133] Performance test:

[0134] The adhesion, wear resistance, water resistance and retroreflective coefficient of the coating composition prepared in Examples 10-12 and Comparative Examples 1-3 were determined according to the standard GA / T 298-2001 "Road marking paint";

[0135] The brightness of the coating composition prepared in Examples 10-12 and Comparative Examples 1-3 was tested after 60 minutes of excitation according to the standard DB33 / T 2204-2019 "Self-luminous traffic sign test procedure";

[0136] The self-repairing time of the coating composition prepared in Examples 1-3 and Comparative Examples 1-3 was tested according to the standard HG / T 5675-2020 "Optical functional film Self-repairing hardening film", and the specific data are shown in Table 1.

[0137] Table 1 - Performance data check table of each sample

[0138]

[0139] Data analysis:

[0140] Comparative analysis of the data in Table 1 above, the adhesion of the coating composition prepared by the present application is 2, the wear amount is 19 mg, the retroreflective coefficient is 264 mcd·(lx·m 2 ) -1The luminance after 60 min of stop excitation is 271 mcd·m -2 and the self-repairing time is 7 min.

[0141] It can be found from the data of comparative example 12 and comparative example 1 that the abrasion resistance, water resistance and luminance after 60 min of stop excitation of the coating composition prepared in example 12 are significantly improved, which indicates that the compatibility of strontium aluminate and whitening polyacrylate is improved after the surface of strontium aluminate is coated with acrylic (hydroxymethyl) ester, the acrylic (hydroxymethyl) ester on the surface of strontium aluminate enhances the crosslinking of whitening polyacrylate as a crosslinking agent, enhances the abrasion resistance of the material, and overcomes the poor water resistance of strontium aluminate, thereby improving the water resistance of the material, and the dispersion performance of strontium aluminate in the coating system is significantly improved after organic modification, thereby improving the stop excitation luminance of the material and ensuring the warning effect of the material at night;

[0142] It can be found from the data of comparative example 12 and comparative example 2 that the abrasion resistance and luminance after 60 min of stop excitation of the coating composition prepared in example 12 are significantly improved, and the self-repairing time is significantly increased, which indicates that by modifying the surface of the self-repairing filler with an epoxy group, the epoxy group is crosslinked with the carboxyl group on the methyl-4-cyclooctene-1-yl carbonate, the carbonate is uniformly dispersed on the self-repairing surface, and then the stable coating structure is formed by self-polymerization and polymerization of the double bond on the surface of the self-repairing filler, which inhibits the self-polymerization reaction of methyl-4-cyclooctene-1-yl carbonate compared with directly solution polymerization, thereby significantly improving the dispersion ability of the functionalized filler, and the transparent polycarbonate component is dispersed in the coating, which greatly improves the ultraviolet absorption ability of strontium aluminate, thereby enhancing the luminance after 60 min of stop excitation, and promoting the activation of the photoinitiator inside the functionalized filler, promoting the self-polymerization repair process of the coated product, and ensuring the improvement of the fluorescence performance of the coated product;

[0143] It can be found by comparing the data of example 12 and comparative example 3 that the adhesion and retroreflective coefficient of the coating composition product prepared in example 12 are significantly reduced, which indicates that after the modification of the polyacrylate organic segment by the epoxy group and the fluorescent whitening group, the epoxy group improves the flowability and wetting behavior of the coating on the substrate, helps to form a more uniform and tight covering layer, thereby improving the adhesion, and the three-membered ring structure of the epoxy group has high reactivity in the ring-opening reaction, which can react through the formation of covalent bonds when the epoxy group contacts the functional groups on the surface of the substrate, thereby greatly improving the adhesion strength of the coating; the fluorescent whitening group excites the electrons to a higher energy level, and then releases energy in the form of long-wavelength light when the electrons fall back to a low energy level, compensates the yellow or dark tone of the material itself after releasing blue light, makes the material look brighter and whiter, and in a lower light environment, the material appears brighter, improves its overall visual appeal, and ensures the eye-catching effect of the coating in the daytime and the warning effect at night;

[0144] Therefore, the present application is to modify the surface of the phosphor to enhance its water resistance and compatibility with organic materials, and after reacting with the whitening polyacrylate as a crosslinking agent, the high light reflection performance of the whitening polyacrylate is enhanced, and the penetration performance of ultraviolet light in the material is enhanced by modifying the transparent material on the surface of the self-repairing material, thereby improving the absorption performance of the phosphor and ultraviolet initiator to ultraviolet light, and finally preparing a coating composition.

[0145] The preferred embodiments of the present application disclosed above are only used to help explain the present application. The preferred embodiments do not describe all the details, nor limit the present application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited only by the claims and their entire scope and equivalents.

Claims

1. A paint composition for pavement marking, characterized by, The raw material composition comprises the following ingredients by weight: 40-60 parts of a whitening polyacrylic acid resin, 20-30 parts of a functionalized filler, and 6-12 parts of an auxiliary material; The functionalized filler is prepared by the following steps: A1, the self-repairing filler, methyl-4-cyclooctene-1-carbonate, triethylamine and N,N-dimethylformamide are added into a reaction kettle, the temperature of the reaction kettle is raised to 60-80 DEG C, and the reaction is kept for 40-60 min, and the functionalized filler precursor is obtained after post-treatment; A2, the functionalized filler precursor and N,N-dimethylformamide are added into an ultrasonic instrument, the frequency of the ultrasonic instrument is set to 10-20 kHz, and after the temperature is raised to 60-80 DEG C, azobisisobutyronitrile is added into the ultrasonic instrument, and the reaction is kept for 1-2 h, and the functionalized filler is obtained after post-treatment; The self-repairing filler is prepared by the following steps: B1, allyl methyl carbonate, triphenyloxy vinyl silane, 4,4'-dimethoxybenzophenone and methyl orthosilicate are added into a reaction kettle and stirred, and the oil phase solution is obtained after stirring for 5-10 min; B2, the oil phase solution is added into an ultrasonic emulsifier, and sorbitan oleate and deionized water are poured into the ultrasonic emulsifier, the frequency of the ultrasonic emulsifier is set to 20-40 kHz, and the mixed emulsion is obtained after ultrasonic treatment for 20-30 min at room temperature; B3, the mixed emulsion is added into a reaction kettle and stirred, saturated sodium hydroxide solution is added dropwise into the reaction kettle to adjust the pH value to 8-10, the temperature of the reaction kettle is raised to 40-50 DEG C, and after keeping for 2-3 h, the temperature of the reaction kettle is reduced to 0-5 DEG C, and the modifier is added in two equal amounts, and after the two additions, the reaction is kept for 1-2 h, and the self-repairing filler is obtained after post-treatment, wherein the modifier is a mixture of vinyl trimethoxysilane and 3-(2,3-epoxypropoxy) propyl trimethoxysilane in a volume ratio of 1 mL:1-1.5 mL; The whitening polyacrylic acid resin is prepared by the following steps: acrylic acid, 1,2-bis(5-methyl-2-benzoxazolyl)-ethylene, 1-allyloxy-2,3-epoxypropane, azobisisobutyronitrile and dimethyl sulfoxide are added into a reaction kettle and stirred, the temperature of the reaction kettle is raised to 60-80 DEG C, and after keeping for 1-2 h, the residual afterglow crosslinking agent and benzoic acid are added into the reaction kettle, and the reaction is kept for 20-30 min, and the whitening polyacrylic acid resin is obtained after post-treatment; The residual afterglow crosslinking agent is prepared by the following steps: C1, 3-(methacryloyloxy) propyl trimethoxysilane and anhydrous ethanol are added into a reaction kettle, stirring is carried out at room temperature for 15 min, and then strontium aluminate is added, the reaction kettle is sealed, and heating is carried out in a water bath at a temperature of 50-60 DEG C for 2-4 h, and the modified strontium aluminate is obtained after post-treatment; C2, the modified strontium aluminate is placed in a reaction kettle containing an acrylic acid(hydroxymethyl) ester / ethylene glycol solution, the temperature of the reaction kettle is raised to 60-80 DEG C, and stirring is carried out while adding potassium persulfate dropwise until flocculent precipitate is generated, and the residual afterglow crosslinking agent is obtained after post-treatment.

2. A paint composition for pavement marking according to claim 1, characterized by In step A1, the ratio of the amounts of self-repairing filler, methyl-4-cyclooctene-1-yl carbonate, triethylamine and N,N-dimethylformamide is 8-10 g:4-5 g:2-3 g:60-70 mL; in step A2, the ratio of the amounts of functionalized filler precursor, N,N-dimethylformamide and azobisisobutyronitrile is 4-5 g:15-20 mL:0.1-0.2 g.

3. The paint composition for pavement marking according to claim 1, characterized by, In step B1, the ratio of the amounts of allyl methyl carbonate, triphenyloxyvinylsilane, 4,4'-dimethoxybenzophenone and tetramethyl orthosilicate is 5-8 g:3-5 g:0.3-0.5 g:20-30 mL; in step B2, the ratio of the amounts of oil phase solution, sorbitan oleate and deionized water is 10-12 mL:3-4 mL:40-60 mL; in step B3, the ratio of the amounts of mixed emulsion and modifier is 40 mL:3-5 mL.

4. The paint composition for pavement marking according to claim 1, wherein The stirring rate of the reaction kettle is 80-120 rpm, and the ratio of the amounts of acrylic acid, 1,2-bis(5-methyl-2-benzoxazolyl)-ethene, 1-allyloxy-2,3-epoxypropane, azobisisobutyronitrile, dimethyl sulfoxide, afterglow crosslinking agent and benzoic acid is 8-10 g:2-3 g:4-5 g:0.3-0.5 g:45-60 mL:2-3 g:0.8-1 g.

5. The paint composition for pavement marking according to claim 1, characterized by In step C1, the stirring rate of the reaction kettle is 80-120 rpm, and the ratio of the amounts of 3-(methacryloyloxy)propyltrimethoxysilane, anhydrous ethanol and strontium aluminate is 4-5 g:40-60 mL:20-30 g; in step C2, the ratio of the amounts of modified strontium aluminate, (hydroxymethyl) acrylate / ethylene glycol solution and potassium persulfate is 4-5 g:20-25 mL:0.3-0.5 g, and the (hydroxymethyl) acrylate / ethylene glycol solution is obtained by mixing (hydroxymethyl) acrylate and ethylene glycol in a ratio of 1 mL:3-5 mL.

6. The method of preparing a paint composition for pavement marking according to any one of claims 1 to 5, characterized in that, The steps include: The whitening polyacrylic acid resin, functionalized repair filler, titanium dioxide, leveling agent, dispersant and ultraviolet absorber are added to the reaction kettle and mixed uniformly, and then passed through a 300-500 mesh screen to obtain a coating composition.

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