Scratch-resistant, mar-resistant, wear-resistant, matte paint and method of making same

Abstract

The application discloses an anti-scratching, non-marking and wear-resistant matte paint and a preparation method thereof, and relates to the technical field of finish paint. The matte paint is prepared by stepwise grafting of components such as modified chlorovinyl acetate resin as a core matrix resin, extinction powder, leveling agent, dispersing agent, solvent, ultraviolet absorber and anti-scratching and wear-resistant agent. The modified chlorovinyl acetate resin takes hydroxyl chlorovinyl acetate resin as a skeleton, is reacted with fluorine-containing acrylic monomer to introduce fluorine-containing unsaturated structure, and is chemically bonded with fluorine-containing aromatic amine to be grafted on the side chain, so that a modified structure with crosslinking activity and fluorination protection function is formed. The preparation method realizes the synergistic optimization of the hardness, wear resistance and salt mist resistance of the paint film.

Description

Technical Field

[0001] This application relates to the technical field of topcoats, and in particular to a scratch-resistant, non-marking, and abrasion-resistant matte paint and its preparation method. Background Technology

[0002] With the upgrading of consumer quality, the market's requirements for the appearance, durability, and environmental adaptability of coated products continue to increase. Chlorovinyl acetate-acrylic resin, a high-performance material composed of a terpolymer of vinyl chloride, vinyl acetate, and acrylate, is gradually becoming the preferred alternative to existing acrylic resins due to the synergistic effect of rigid chlorine segments, flexible vinyl acetate units, and functional acrylic groups in its molecular structure. In daily life and mass production, various coated products are subjected to complex conditions of high-frequency friction, minor impacts, and temperature fluctuations. The cured film of chlorovinyl acetate-acrylic resin perfectly adapts to these harsh environments, and its performance advantages continue to stand out. In the home furnishing sector, products such as wardrobes, cabinets, metal handles, and plastic appliance casings are frequently subjected to human touch, wiping and cleaning, friction from clothing, and minor scratches from hard objects such as keys and jewelry. The cured film of chlorovinyl acetate-acrylic resin has high hardness and excellent wear resistance, making it less prone to scratches of varying depths and effectively maintaining the integrity of the coating. However, chloroacetic acid acrylic resin also has certain application limitations. Due to its molecular structure, its paint film has relatively weak low-temperature toughness and is prone to cracking in low-temperature environments, making it unsuitable for low-temperature conditions. Furthermore, the resin itself is highly polar, resulting in poor adhesion to some non-polar substrates, often requiring additional substrate treatment before coating. In addition, the weather resistance of this resin system is inferior to pure acrylic resin; after prolonged outdoor exposure, the coating is prone to yellowing and chalking. Moreover, its formulation flexibility is limited, and its compatibility with certain additives and colorants is generally poor, increasing the difficulty of coating research and development and production.

[0003] In particular, in coastal areas with high salt spray or in northern winters where de-icing agents are applied to roads, ordinary paint films face even more severe corrosion challenges. For example, when vehicles are parked at docks for extended periods, high concentrations of salt spray carried by sea breezes continuously settle on the paint surface. In addition, mechanical damage such as cargo collisions and forklift scraping during loading and unloading operations damages the integrity of the paint film, causing pitting corrosion to occur in a short period of time and quickly spread into large-area rust. Furthermore, in northern winters, chloride-based de-icing agents applied by vehicles are splashed onto chassis components by the wheels, forming a strong electrolyte solution in low-temperature and humid environments, accelerating the corrosion process. Ordinary acrylic resins, due to their insufficient linear molecular structure density and limited adhesion to metal substrates, are unable to prevent the longitudinal penetration and lateral spread of corrosive media, leading to protective failure. In addition, in the loading and unloading platform area of ​​the cold chain logistics warehouse, the frequent entry and exit of forklifts brings about a drastic temperature difference between indoors and outdoors. The paint surface experiences repeated switching between the -18 degree Celsius cold storage environment and the normal temperature environment. The internal stress generated by thermal expansion and contraction causes the paint film to gradually de-adhere to the substrate interface. After the edges lift up, corrosion channels are formed. At the same time, the sand and gravel particles carried by the forklift tires roll and slide on the low-temperature hardened paint surface, causing dense scratches and further weakening the protective performance. Summary of the Invention

[0004] The purpose of this application is to provide a scratch-resistant, non-marking, and abrasion-resistant matte paint and its preparation method. The matte paint prepared by this method has excellent abrasion resistance, scratch resistance, non-marking properties, excellent corrosion resistance, and hardness.

[0005] Firstly, the scratch-resistant, non-marking, and wear-resistant matte paint and its preparation method provided in this application adopt the following technical solution: A scratch-resistant, non-marking, and wear-resistant matte paint comprises the following components by weight: 50-75 parts modified chloroacetic acid resin, 3-6 parts matting agent, 0.1-1 parts silicone leveling agent, 0.5-2 parts acrylate leveling agent, 1-2 parts first dispersant, 1-2 parts second dispersant, 10-15 parts co-solvent, 10-20 parts main solvent, 0.5-1 parts ultraviolet absorber, and 1-2 parts anti-scratch and wear-resistant agent; wherein the modified chloroacetic acid resin comprises: hydroxyl chloroacetic acid resin, a carboxyl-containing monomer I, and an amino-containing monomer II; wherein the mass ratio of the hydroxyl chloroacetic acid resin, the carboxyl-containing monomer I, and the amino-containing monomer II is 1:(0.5-0.9):(0.6-1.3).

[0006] By adopting the above technical solution, modified chlorovinyl acetate resin is grafted with hydroxychlorovinyl acetate resin as the backbone, introducing carboxyl-containing monomer one and amino-containing monomer two for modification. This intramolecular / intermolecular crosslinking significantly enhances the resin's cohesive strength and coating toughness, allowing the paint film to absorb energy through elastic deformation rather than brittle fracture when subjected to external scratches, thus achieving excellent scratch-resistant and non-marking performance. Simultaneously, the introduction of amino and carboxyl groups improves the resin's wetting and anchoring ability on the surfaces of inorganic or organic fillers such as matting agents and anti-scratch and abrasion-resistant agents, avoiding paint film defects caused by sedimentation and agglomeration, resulting in a uniform and delicate matte effect. The polar groups of the modified resin also enhance adhesion to the substrate and strengthen the low-temperature mobility of molecular chain segments. Combined with a suitable amount of co-solvent and main solvent evaporation design, the paint film can still achieve sufficient leveling and dense crosslinking at low temperatures, balancing low-temperature application adaptability and paint film integrity. Meanwhile, the combination of silicone leveling agent and acrylic leveling agent effectively reduces surface tension and eliminates defects such as orange peel and pinholes. The introduction of ultraviolet absorber works synergistically with the weather-resistant groups of the modified resin to delay photo-aging degradation and ensure that the matte coating maintains stable decorative and protective functions during long-term outdoor use.

[0007] Optionally, the modified chloroacetic acid resin is obtained through the following preparation steps: S1. Mix hydroxychloroacetic acid resin, carboxyl-containing monomer 1 with toluene, stir, add p-toluenesulfonic acid and polymerization inhibitor, heat, stir, and distill under reduced pressure to obtain intermediate; S2. The intermediate is mixed with the amino-containing monomer di-N,N-dimethylformamide, potassium carbonate is added, the mixture is heated, stirred, and distilled under reduced pressure to obtain the modified chloroacetic acid resin.

[0008] By adopting the above technical solution, in the first step, under the catalysis of p-toluenesulfonic acid, hydroxychloroacetic acid resin reacts with carboxyl-containing monomer one in toluene solvent. The active group in carboxyl-containing monomer one chemically bonds with the resin chain segment, introducing a fluorinated unsaturated structure into the resin skeleton. After removing the solvent and small molecule byproducts by vacuum distillation, an intermediate is obtained. In the second step, the intermediate reacts with amino-containing monomer two in N,N-dimethylformamide under the condition of potassium carbonate as an acid-binding agent. The amino group in amino-containing monomer two chemically bonds with the active site on the intermediate, grafting a fluorinated aryl structure onto the resin chain segment. After purification by vacuum distillation, modified chloroacetic acid resin is obtained.

[0009] Optionally, the carboxyl-containing monomer is a mixture of 2-fluoroacrylic acid and 2-(trifluoromethyl)acrylic acid in a mass ratio of 1:(1-3).

[0010] By employing the above technical solution, using 2-fluoroacrylic acid and 2-(trifluoromethyl)acrylic acid in a specific ratio as a carboxyl-containing monomer, its technical value lies in achieving synergistic enhancement of resin performance through different introduction methods of fluorine. 2-fluoroacrylic acid directly replaces the olefin hydrogen with a single fluorine atom, imparting appropriate polarity and steric hindrance to the resin chain segments, exhibiting good reactivity in chemical bonding reactions, ensuring that the double bond can be efficiently integrated into the chloroacetic acid resin backbone, providing sufficient reaction sites for subsequent cross-linking and curing. 2-(trifluoromethyl)acrylic acid is introduced in the form of a trifluoromethyl side group. This group is large and rich in fluorine atoms, enabling it to migrate and accumulate on the paint film surface after resin curing, forming a low-surface-energy fluorinated protective layer. When used in combination, the single fluorine structure ensures reaction efficiency and cross-linking density, while the trifluoromethyl structure dominates surface performance regulation, giving the paint film both excellent chemical resistance and anti-fouling self-cleaning properties. In addition, the strong electronegativity of fluorine atoms effectively reduces the surface tension of resin segments. Combined with the leveling agent system, it can significantly improve the leveling and spreading properties under low temperature conditions, ultimately enabling matte paint to achieve outstanding weather resistance and durability while maintaining an elegant appearance.

[0011] Optionally, the amino-containing monomer II is any one or more of 2,4,5-trifluoroaniline and 4-aminotrifluorotoluene.

[0012] By employing the above technical solution, the amino group of 2,4,5-trifluoroaniline is directly attached to the benzene ring, and the three fluorine atoms are distributed at different sites on the benzene ring. This polyfluorinated substitution structure provides moderate nucleophilic activity of the amino group, making it easy to control the reaction rate during substitution reactions with the intermediate active chlorine and avoiding excessive cross-linking. Simultaneously, the rigid structure of the polyfluorinated benzene ring, after being incorporated into the resin side chain, enhances the hardness and heat resistance of the coating film. The high bond energy of the fluorine atoms also strengthens the coating's weather resistance and resistance to media erosion. In contrast, 4-aminotrifluorotoluene uses a trifluoromethyl group as the fluorine carrier. This group has a larger volume and a high electron cloud density, making it easier to migrate and accumulate on the coating film surface after being incorporated into the resin, forming a denser fluorinated hydrophobic barrier and endowing the coating with excellent hydrophobic, oleophobic, and antifouling self-cleaning properties. Its para-substitution structure of the benzene ring also results in better molecular symmetry, which is beneficial for the regular arrangement of resin chain segments and improves the film density under low-temperature conditions.

[0013] Optionally, in step S1, the heating temperature is 90-110℃ and the heating time is 4-6h; in step S2, the heating temperature is 60-80℃ and the heating time is 6-10h.

[0014] By adopting the above technical solution, step S1 uses a higher temperature and a medium duration, which is conducive to accelerating chemical bonding and promoting the efficient insertion of double bonds into the resin backbone, while avoiding side reactions or resin degradation caused by overheating; step S2 lowers the temperature and extends the time, which takes into account the binding of amino groups to active sites, prevents side reactions such as amino oxidation or dehalogenation at high temperatures, and ensures that the grafting reaction proceeds smoothly and the product structure is controllable.

[0015] Optionally, the co-solvent is any one of xylene, ethylene glycol monobutyl ether, and diacetone alcohol.

[0016] By adopting the above technical solutions, xylene, as an aromatic solvent, has excellent compatibility with modified chloroacetic acid resin, which can effectively reduce the viscosity of the system and promote the full dissolution of the resin; ethylene glycol monobutyl ether has both ether bonds and hydroxyl groups, which can not only help dissolve polar components, but also slow down the surface drying speed of the paint film and improve leveling; diacetone alcohol contains ketone alcohol bifunctional groups, which have good wetting and dispersing effects on matting powder and additives, and can adjust the volatility gradient.

[0017] Optionally, the main solvent is any one of butyl acetate, ethyl acetate, and propylene glycol methyl ether acetate.

[0018] By adopting the above technical solutions, butyl acetate has a high boiling point, which can slow down the drying process of the paint film and provide sufficient leveling time; ethyl acetate evaporates quickly, which is conducive to rapid surface drying in low-temperature environments and improves construction efficiency; propylene glycol methyl ether acetate, as an ether-ester mixed solvent, has better wetting properties for polar resins and additives, and has low toxicity and outstanding environmental friendliness.

[0019] Optionally, the acrylate leveling agent is any one or more of fluorine-modified polyacrylate leveling agents and phosphate-modified polyacrylate leveling agents.

[0020] By adopting the above technical solutions, fluorinated modified polyacrylates, with their extremely low surface tension characteristics of fluorine atoms, can significantly reduce the surface energy of the paint film, effectively eliminate defects such as orange peel and pinholes, and endow the coating with a certain water-repellent and anti-fouling ability; phosphate modified polyacrylates utilize the chelating and anchoring effect of phosphate groups on the metal substrate, which improves leveling while enhancing the adhesion and corrosion resistance of the paint film.

[0021] Secondly, the scratch-resistant, non-marking, and wear-resistant matte paint and its preparation method provided in this application adopt the following technical solution: A scratch-resistant, non-marking, and wear-resistant matte paint and its preparation method, comprising the following steps: Step 1: Mix the first dispersant, the second dispersant, the cosolvent, and the main solvent, stir, and add the modified chloroacetic acid resin to obtain the mixture; Step 2: Add matte powder and anti-scratch and abrasion resistant agent to the mixture, stir evenly, grind, add silicone leveling agent, acrylic leveling agent and UV absorber, stir evenly, and you will get scratch-resistant, non-marking and abrasion resistant matte paint.

[0022] By adopting the above technical solution, the dual dispersant is first premixed with the solvent system. The fully extended conformation of the dispersant in the liquid phase establishes a basis for steric hindrance and electrostatic stability. Then, the modified chloroacetic acid resin is introduced to ensure that the resin molecular chains are fully swollen and uniformly dispersed by the solvent, avoiding agglomeration due to excessively high local concentrations when powder is added later. Subsequently, matting powder and anti-scratch and abrasion-resistant agent are added and a grinding process is carried out. The mechanical shearing force is used to refine the filler to a suitable particle size. At the same time, the dual dispersant works synergistically to maintain its highly dispersed state and prevent sedimentation or flocculation. In the final stage, silicone leveling agent, acrylate leveling agent and ultraviolet absorber are added to avoid these low-dosage additives from being damaged or ineffective in the early high-speed shearing or being over-adsorbed on the powder surface, ensuring that they act precisely on the paint film surface to perform leveling and weather resistance functions.

[0023] Thirdly, the application of the scratch-resistant, non-marking, and wear-resistant matte paint provided in this application Application of a scratch-resistant, non-marking, and wear-resistant matte paint in automotive interiors, 3C products, plastic products for home appliances, and hardware products.

[0024] In summary, this application includes at least one of the following beneficial technical effects: 1. Compared with existing technologies, this application prepares modified chloroacetic acid resin through a stepwise method. First, fluorinated acrylic acid monomers are chemically bonded to hydroxychloroacetic acid resin to introduce unsaturated double bonds into the resin backbone. Then, fluorinated aromatic amines are chemically bonded to the side chains to form a modified structure with both crosslinking activity and fluorination protection. After curing, the modified resin forms a highly entangled three-dimensional crosslinked network, which significantly improves the cohesive strength and wear resistance of the coating film. At the same time, the abundant carbon-fluorine bonds on the side chains migrate and accumulate on the coating surface to form a dense low surface energy barrier layer, effectively blocking the penetration of salt spray corrosion media. This endows the coating with excellent chemical inertness and hydrophobic antifouling ability, achieving synergistic optimization of hardness, wear resistance, and salt spray resistance. 2. Compared with existing technologies, this application utilizes a synergistic compounding system of modified vinyl chloride resin, matting agent, silicone leveling agent, acrylate leveling agent, bi-dispersant system, co-solvent and main solvent, UV absorber, and scratch-resistant and abrasion-resistant agent. Each component complements the other to form a complete protective system. The bi-dispersant ensures high dispersion and non-settling of the matting agent and scratch-resistant and abrasion-resistant agent; the compounding of silicone and acrylate leveling agent eliminates surface defects and reduces surface tension; the volatile gradient design of the co-solvent and main solvent ensures leveling and cross-linking density at low temperatures; and the UV absorber, in conjunction with the weather-resistant groups of the modified resin, delays photoaging. Ultimately, this allows the matte paint to maintain a uniform and delicate matte appearance while possessing excellent scratch resistance, low-temperature toughness, and long-term weather resistance stability. Detailed Implementation

[0025] Unless otherwise specified, all raw materials used in the embodiments and comparative examples of this application are commercially available products: 2,4,5-Trifluoroaniline, CAS No.: 367-34-0; Aminotrifluorotoluene, CAS No.: 455-14-1; 2-Amino-5-fluorotrifluorotoluene, CAS No.: 393-39-5; Hydroxychloroethylene resin, brand name: VAGH, Dow Chemical; BYK161, purchased from BYK Chemicals, Germany; TEGO Dispers 3, purchased from TEGO Chemicals, Germany; Matte powder, model: ACEMATT HK 440, Evonik, Germany; Anti-scratch and abrasion resistant compound, model: Ceridust 3943F, Clariant; Silicone leveling agent, model: BYK-333, manufactured by BYK Chemicals, Germany; Acrylic leveling agent, model: BYK-358, BYK Chemicals, Germany; Ultraviolet absorber, model: Tinuvin 326, BASF.

[0026] Example 1 A scratch-resistant, non-marking, and wear-resistant matte paint and its preparation method, comprising the following steps: The first step is to prepare the modified chlorinated vinyl resin. Three parts by weight of hydroxychloroacetic acid resin, one part by weight of 2-fluoroacrylic acid, 1.4 parts by weight of 2-(trifluoromethyl)acrylic acid, and 55 ml of toluene were mixed and stirred at 300 rpm for 5 min to obtain a first mixture. 0.2 parts by weight of p-toluenesulfonic acid and 0.03 parts by weight of p-hydroxyanisole were added to the first mixture, and the mixture was heated to 90 °C and stirred at 500 rpm for 5 h to obtain a second mixture. The second mixture was distilled at -0.08 MPa and 60 °C for 5 h, and the product was collected to obtain an intermediate.

[0027] 3.5 parts by weight of the intermediate, 2.4 parts by weight of 2,4,5-trifluoroaniline, and 80 parts by weight of N,N-dimethylformamide were mixed and stirred at 300 rpm for 5 min to obtain a third mixture. 0.1 parts by weight of potassium carbonate were added to the third mixture, and the mixture was heated to 70 °C and stirred at 300 rpm for 6 h to obtain a fourth mixture. The fourth mixture was distilled at -0.08 MPa and 95 °C for 7 h, and the product was collected to finally obtain the modified chloroacetic acid resin.

[0028] The second step is to prepare a scratch-resistant, non-marking, and wear-resistant matte paint. 1.5 parts by weight of BYK161 (first dispersant), 1.5 parts by weight of TEGO Dispers 3 (second dispersant), 12.5 parts by weight of xylene, and 15 parts by weight of propylene glycol methyl ether acetate were mixed and stirred at 260 rpm for 10 min. While stirring, 70 parts by weight of modified chloroacetic acid resin were added and stirred at 300 rpm for 10 min to obtain the mixture.

[0029] Add 4.5 parts by weight of matte powder and 1.5 parts by weight of scratch-resistant and abrasion-resistant agent to the mixture, and stir at 800 rpm for 30 minutes. Circulate and grind the material at 1200 rpm for 0.5 hours, obtaining a grinding fineness of 5 μm. Reduce the stirring speed to 250 rpm, and while stirring, add 0.5 parts by weight of silicone leveling agent, 1 part by weight of acrylic leveling agent, and 0.75 parts by weight of UV absorber. Stir at 250 rpm for 10 minutes to obtain a scratch-resistant, non-marking, and abrasion-resistant matte paint. Example 2

[0030] The difference between Example 2 and Example 1 is that the 3 parts by weight of hydroxychloroacetic acid resin, 1 part by weight of 2-fluoroacrylic acid, 1.4 parts by weight of 2-(trifluoromethyl)acrylic acid, and 2.4 parts by weight of 2,4,5-trifluoroaniline in Example 1 are replaced with 3 parts by weight of hydroxychloroacetic acid resin, 0.625 parts by weight of 2-fluoroacrylic acid, 0.875 parts by weight of 2-(trifluoromethyl)acrylic acid, and 1.8 parts by weight of 2,4,5-trifluoroaniline. Example 3

[0031] The difference between Example 3 and Example 1 is that 3 parts by weight of hydroxychloroacetic acid resin, 1 part by weight of 2-fluoroacrylic acid, 1.4 parts by weight of 2-(trifluoromethyl)acrylic acid, and 2.4 parts by weight of 2,4,5-trifluoroaniline in Example 1 are replaced with 3 parts by weight of hydroxychloroacetic acid resin, 0.75 parts by weight of 2-fluoroacrylic acid, 1.05 parts by weight of 2-(trifluoromethyl)acrylic acid, and 2.4 parts by weight of 2,4,5-trifluoroaniline. Example 4

[0032] The difference between Example 4 and Example 1 is that 3 parts by weight of hydroxychloroacetic acid resin, 1 part by weight of 2-fluoroacrylic acid, 1.4 parts by weight of 2-(trifluoromethyl)acrylic acid, and 2.4 parts by weight of 2,4,5-trifluoroaniline in Example 1 are replaced with 3 parts by weight of hydroxychloroacetic acid resin, 1.125 parts by weight of 2-fluoroacrylic acid, 1.575 parts by weight of 2-(trifluoromethyl)acrylic acid, and 3.3 parts by weight of 2,4,5-trifluoroaniline. Example 5

[0033] The difference between Example 5 and Example 3 is that 2,4,5-trifluoroaniline in Example 3 is replaced with 4-aminotrifluorotoluene in 2.4 parts by weight. Example 6

[0034] The difference between Example 6 and Example 5 is that 0.75 parts by weight of 2-fluoroacrylic acid and 1.05 parts by weight of 2-(trifluoromethyl)acrylic acid in Example 5 are replaced with 0.9 parts by weight of 2-fluoroacrylic acid and 0.9 parts by weight of 2-(trifluoromethyl)acrylic acid. Example 7

[0035] The difference between Example 7 and Example 5 is that 0.75 parts by weight of 2-fluoroacrylic acid and 1.05 parts by weight of 2-(trifluoromethyl)acrylic acid in Example 5 are replaced with 0.45 parts by weight of 2-fluoroacrylic acid and 1.35 parts by weight of 2-(trifluoromethyl)acrylic acid. Comparative Example 1

[0036] The difference between Comparative Example 1 and Example 1 is that 3 parts by weight of hydroxychloroacetic acid resin, 1 part by weight of 2-fluoroacrylic acid, 1.4 parts by weight of 2-(trifluoromethyl)acrylic acid, and 2.4 parts by weight of 2,4,5-trifluoroaniline in Example 1 are replaced with 3 parts by weight of hydroxychloroacetic acid resin, 0.742 parts by weight of 2-fluoroacrylic acid, 0.964 parts by weight of 2-(trifluoromethyl)acrylic acid, and 4 parts by weight of 2,4,5-trifluoroaniline. Comparative Example 2

[0037] The difference between Comparative Example 2 and Example 3 is that 2,4,5-trifluoroaniline in 2.4 parts by weight in Example 3 is replaced with 2-amino-5-fluorotrifluorotoluene. Comparative Example 3

[0038] The difference between Comparative Example 3 and Example 5 is that 0.75 parts by weight of 2-fluoroacrylic acid and 1.05 parts by weight of 2-(trifluoromethyl)acrylic acid in Example 3 were replaced with 0.3 parts by weight of 2-fluoroacrylic acid and 1.5 parts by weight of 2-(trifluoromethyl)acrylic acid. Comparative Example 4

[0039] The difference between Comparative Example 4 and Example 5 lies in the different preparation methods of the modified chloroacetic acid resin.

[0040] Three parts by weight of hydroxychloroacetic acid resin, 0.75 parts by weight of 2-fluoroacrylic acid, 1.05 parts by weight of 2-(trifluoromethyl)acrylic acid, 2.4 parts by weight of 4-aminotrifluorotoluene, and 55 ml of toluene were mixed and stirred at 300 rpm for 5 min. Then, 0.2 parts by weight of p-toluenesulfonic acid, 0.03 parts by weight of p-hydroxyanisole, and 0.1 parts by weight of potassium carbonate were added. The mixture was heated to 90 °C and stirred at 500 rpm for 3 h. Subsequently, 80 parts by weight of N,N-dimethylformamide were added, and the mixture was cooled to 55 °C and stirred at 300 rpm for 6 h. After the reaction was completed, the product was collected by vacuum distillation to obtain the modified chloroacetic acid resin. Comparative Example 5

[0041] The difference between Comparative Example 5 and Example 5 is that the modified chloroacetic acid resin in Example 5 is replaced with unmodified hydroxychloroacetic acid resin (commercially available).

[0042] Test case The scratch-resistant, non-marking, and abrasion-resistant matte paints prepared in Examples 1-7 and Comparative Examples 1-5 were sprayed onto polycarbonate films, with a film thickness of 20 μm. The films were then cured at 70°C for 60 min. Abrasion resistance: The abrasion resistance of the cured samples was tested in accordance with GB / T 1768-2006 "Determination of abrasion resistance of paints and varnishes - Rotary rubber grinding wheel method". Salt spray resistance: Salt spray test was conducted on the cured samples in accordance with GB / T 1771-2007 "Determination of resistance to neutral salt spray of paints and varnishes"; Hardness: The hardness of the cured samples was tested according to GB / T 6739-2022 "Determination of Hardness of Paints and Varnishes by Pencil Method". The test results are shown in Table 1.

[0043] By comparing and analyzing Examples 1-4 and Comparative Example 1, it was found that the product prepared in Example 3 had the best performance. The reason for this performance difference may be the different mass ratios of hydroxychloroacetic acid resin, 2-fluoroacrylic acid, 2-(trifluoromethyl)acrylic acid, and 2,4,5-trifluoroaniline. When the amount of carboxyl-containing monomer is too low, the number of double bonds chemically bonded to the resin backbone is insufficient, reducing the number of active sites that can participate in the crosslinking reaction in the subsequent curing stage. This results in a sparse crosslinking network in the paint film, decreased cohesive strength, and consequently, reduced hardness and abrasion resistance. At the same time, insufficient fluorine introduction makes it difficult to form a continuous and dense fluorinated barrier layer on the paint film surface, thus reducing salt spray resistance. When the amount of amino monomer II is too high, exceeding the equivalent of active chlorine on the resin chain segments, the excess amino monomer cannot be effectively grafted and remains in the paint film system, acting as a plasticizer. This weakens the interaction forces between molecular chains, reducing the hardness and density of the paint film. Simultaneously, unreacted small molecules are easily dissolved by moisture in a salt spray environment, forming microporous channels and accelerating the penetration of corrosive media into the substrate, severely impairing salt spray resistance. Conversely, when the amount of carboxyl monomer I is too high, although the introduction of double bonds increases, the excessively high grafting density makes the resin chain segments too rigid and lacking in flexibility. The paint film is prone to brittle fracture rather than elastic deformation under external force, which is detrimental to improving wear resistance. In Example 3, the proportions of each component are at the optimal balance point, with high conversion rates of chemical bonding reactions and chemical bonding. The double bond density and fluorinated group distribution on the resin chain segments are moderate, resulting in a dense network structure with suitable crosslinking density and rich in CF bonds after curing, thus balancing the hardness, wear resistance, and salt spray resistance of the paint film.

[0044] Comparative analysis of Examples 3, 5, and Comparative Example 2 revealed that the product prepared in Example 5 exhibited the best overall performance. The difference in performance may be attributed to the different amino-containing monomers. Example 5 used 4-aminotrifluorotoluene with trifluoromethyl as the fluorine carrier. This group has a large volume and strong hydrophobicity. After grafting onto the resin side chains, it tends to migrate and accumulate on the paint film surface during curing, forming a continuous, dense, low-surface-energy fluorinated barrier layer. This effectively blocks the penetration of corrosive media such as salt spray. Simultaneously, its para-substitution structure ensures good molecular symmetry, which is beneficial for the regular arrangement and tight stacking of resin segments, giving the paint film high hardness and wear resistance. Although the 2,4,5-trifluoroaniline used in Example 3 contains three fluorine atoms on the benzene ring, and its rigid structure helps improve hardness, the fluorine atoms are dispersed at different sites on the benzene ring rather than concentrated in one group. Its surface migration and accumulation ability is not as good as that of trifluoromethyl, resulting in a slightly inferior uniformity and density of the formed fluorinated protective layer, and slightly insufficient salt spray resistance. Although the 2-amino-5-fluorotrifluorotoluene used in Comparative Example 2 contains both cyclic fluorine and trifluoromethyl, the spatial arrangement of its ortho-amino and meta-fluorine atoms leads to an asymmetric distribution of molecular polarity. After grafting, the resin chain segments are poorly arranged, the intermolecular stacking is loose, the film density decreases, and the hardness and wear resistance are reduced. Furthermore, the asymmetric structure is not conducive to the orderly arrangement of fluorinated groups on the surface, and the salt spray barrier effect is significantly weakened.

[0045] Comparative analysis of Examples 5-7 and Comparative Example 3 revealed that the product prepared in Example 5 exhibited the best overall performance. The difference in performance may be attributed to the varying mass ratios of 2-fluoroacrylic acid and 2-(trifluoromethyl)acrylic acid. 2-fluoroacrylic acid, with its small molecular size and low steric hindrance, possesses high reactivity in chemical bonding reactions, ensuring efficient incorporation of double bonds into the resin backbone and providing ample active sites for curing and crosslinking. Conversely, 2-(trifluoromethyl)acrylic acid, through its trifluoromethyl side groups, introduces a large amount of fluorine, dominating the construction of the fluorinated layer on the paint film surface. When the proportion of 2-(trifluoromethyl)acrylic acid is too high, its significant steric hindrance substantially reduces the chemical bonding conversion rate, leading to insufficient double bond grafting density, a sparse crosslinking network, and decreased hardness and abrasion resistance. Furthermore, unreacted monomer residues also weaken salt spray resistance. Example 5 demonstrated a suitable ratio of 2-fluoroacrylic acid to fluorine content, resulting in optimal overall performance.

[0046] A comparative analysis of Example 5 and Comparative Example 4 revealed that the product prepared in Example 5 exhibited superior overall performance. This difference is likely due to variations in the preparation methods of the modified chloroacetic acid resin. Example 5 employed a stepwise method, first completing the chemical bonding reaction between hydroxyl and carboxyl groups under the catalysis of p-toluenesulfonic acid, and then performing the chemical bonding of amino groups to active chlorine under the action of potassium carbonate. The reaction conditions for each step were independently optimized, resulting in high conversion rates and well-defined product structures. Comparative Example 4 conducted the chemical bonding and substitution reactions in the same system. The coexistence of p-toluenesulfonic acid and potassium carbonate led to acid-base neutralization, consuming both catalysts and causing them to lose their catalytic activity. This resulted in a significant decrease in the double bond grafting rate during the chemical bonding reaction. Furthermore, the amino group may undergo competitive amidation with the carboxyl group under high-temperature acidic conditions, consuming the carboxyl monomer intended for chemical bonding. Consequently, the final product exhibited severely insufficient double bond density and fluorinated group grafting, resulting in a sparse crosslinking network lacking CF bond protection after curing. The film hardness, abrasion resistance, and salt spray resistance were significantly inferior to the product prepared by the stepwise method.

[0047] A comparative analysis of Example 5 and Comparative Example 5 revealed that the product prepared in Example 5 exhibited superior overall performance. This difference is likely due to the specific modification of the chloroacetic acid resin employed in Example 5. Example 5 grafted fluorinated acrylic monomers onto the resin backbone via chemical bonding, introducing numerous unsaturated double bonds. These double bonds, during the curing stage, copolymerized and crosslinked with other components in the system, forming a highly entangled three-dimensional network structure, significantly enhancing the cohesive strength and abrasion resistance of the coating film. Simultaneously, fluorinated aromatic amines were grafted onto the side chains via chemical bonding, introducing abundant CF bonds. These high-energy, low-polarity chemical bonds endowed the coating film with excellent chemical inertness and hydrophobic barrier function, effectively resisting the penetration and erosion of salt spray media. In contrast, Comparative Example 5 directly used unmodified hydroxychloroacetic acid resin, whose molecular chains lacked both double bonds participating in crosslinking and curing, and fluorinated groups providing chemical protection. The coating film relied solely on physical drying, resulting in extremely low crosslinking density and significantly deteriorated hardness, abrasion resistance, and salt spray resistance.

[0048] The above are all preferred embodiments of this application, and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made to the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A scratch-resistant, non-marking, and wear-resistant matte paint, characterized in that, The product comprises the following components by weight: 50-75 parts modified chloroacetic acid resin, 3-6 parts matting agent, 0.1-1 parts silicone leveling agent, 0.5-2 parts acrylate leveling agent, 1-2 parts primary dispersant, 1-2 parts secondary dispersant, 10-15 parts co-solvent, 10-20 parts primary solvent, 0.5-1 parts ultraviolet absorber, and 1-2 parts anti-scratch and abrasion resistant agent; the modified chloroacetic acid resin comprises: hydroxyl chloroacetic acid resin, a carboxyl-containing monomer I, and an amino-containing monomer II; the mass ratio of the hydroxyl chloroacetic acid resin, the carboxyl-containing monomer I, and the amino-containing monomer II is 1:(0.5-0.9):(0.6-1.3).

2. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1, characterized in that, The modified chloroacetic acid resin is obtained through the following preparation steps: S1. Mix hydroxychloroacetic acid resin, carboxyl-containing monomer 1 with toluene, stir, add p-toluenesulfonic acid and polymerization inhibitor, heat, stir, and distill under reduced pressure to obtain intermediate; S2. The intermediate is mixed with the amino-containing monomer di-N,N-dimethylformamide, potassium carbonate is added, the mixture is heated, stirred, and distilled under reduced pressure to obtain the modified chloroacetic acid resin.

3. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1 or 2, characterized in that, The carboxyl-containing monomer is a mixture of 2-fluoroacrylic acid and 2-(trifluoromethyl)acrylic acid in a mass ratio of 1:(1-3).

4. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1 or 2, characterized in that, The amino-containing monomer II is any one or more of 2,4,5-trifluoroaniline and 4-aminotrifluorotoluene.

5. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 2, characterized in that, In step S1, the heating temperature is 90-110℃ and the heating time is 4-6h; in step S2, the heating temperature is 60-80℃ and the heating time is 6-10h.

6. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1, characterized in that, The co-solvent is any one of xylene, ethylene glycol monobutyl ether, and diacetone alcohol.

7. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1, characterized in that, The main solvent is any one of butyl acetate, ethyl acetate, and propylene glycol methyl ether acetate.

8. The scratch-resistant, non-marking, and wear-resistant matte paint according to claim 1, characterized in that, The acrylate leveling agent is any one or more of fluorine-modified polyacrylate leveling agents and phosphate-modified polyacrylate leveling agents.

9. A method for preparing a scratch-resistant, non-marking, and abrasion-resistant matte paint as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Mix the first dispersant, the second dispersant, the cosolvent, and the main solvent, stir, and add the modified chloroacetic acid resin to obtain the mixture; Step 2: Add matte powder and anti-scratch and abrasion resistant agent to the mixture, stir evenly, grind, add silicone leveling agent, acrylic leveling agent and UV absorber, stir evenly, and you will get scratch-resistant, non-marking and abrasion resistant matte paint.

10. The application of a scratch-resistant, non-marking, and abrasion-resistant matte paint as described in any one of claims 1-8 in automotive interiors, 3C products, plastic products for home appliances, and hardware products.

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