High-stability antibacterial acrylic coating composition and preparation method thereof

Abstract

The invention relates to a high-stability antibacterial acrylic coating composition and a preparation method thereof, the high-stability antibacterial acrylic coating composition is prepared from the following raw materials: modified acrylic resin, epoxy resin, a silane polymer, a filler, an auxiliary agent and a solvent, the invention relates to a water-based acrylate adhesive which is a product obtained by free radical polymerization of N-phenylmaleimide, butyl acrylate, zinc acrylate and acrylate of silicon dioxide coupled with a fluoroalkyl chain. According to the high-stability antibacterial acrylic coating composition, fluorine-containing groups are introduced through the 2-fluoroacrylic acid, so that the stability of the coating composition is improved, the stability of the coating composition is further improved through the introduced N-phenylmaleimide, a cytoplasmic membrane can be ruptured, the high-stability antibacterial acrylic coating composition has good antibacterial performance, the compatibility of all the components is good, and the high-stability antibacterial acrylic coating composition is suitable for large-scale popularization and application. And a synergistic effect is generated, so that the coating composition has good comprehensive properties such as antibacterial property, stability and the like, and has a good application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, in particular to a highly stable antibacterial acrylic coating composition and a preparation method thereof. Background Art

[0002] Acrylic paint is a coating system based on acrylic resin with fillers, solvents, additives, etc. Among them, commonly used types of acrylic resins include thermoplastic acrylic resins, thermosetting acrylic resins, modified resins, etc., commonly used fillers include montmorillonite, silica, calcined kaolin, talc, calcium carbonate, diatomaceous earth, etc., commonly used solvents include toluene, xylene, ethyl acetate, butyl acetate, ethanol, n-butanol, acetone, methyl isobutyl ketone, etc., and commonly used additives include silicones, acrylate additives, etc.

[0003] Common acrylic coatings can be divided into thermoplastic acrylic coatings and thermosetting acrylic coatings according to their film-forming mechanism. Among them, thermoplastic acrylic coatings have medium hardness (pencil hardness HB-2H), good flexibility (can bend without cracking), good weather resistance, and are not prone to powdering or yellowing after long-term outdoor use (better than alkyd resins and close to polyurethane). They are suitable for scenes with high requirements for color retention (such as billboards and plastic shell coatings); thermosetting acrylic coatings have high hardness (up to 3H or more), are scratch-resistant and solvent-resistant (not easy to fall off when wiped with gasoline or engine oil), and have a certain degree of resistance to acid, alkali, and salt corrosion. They are suitable for industrial corrosion protection (such as construction machinery and containers) and high-performance coatings (original automotive paint and high-end building exteriors).

[0004] However, there are also some problems with the common acrylic coatings currently available, such as: (1) The stability is not high enough. In complex environments, including industrial high-temperature equipment and components, ships, marine engineering and transportation facilities, chemical and industrial anti-corrosion fields, etc., acrylic coatings need to have good stability, including heat resistance, weather resistance, corrosion resistance, etc.; (2) The antibacterial performance is not enough. In some scenarios where coatings need to have antibacterial properties, including hospital walls / floors, medical equipment, food workshop walls / equipment, kitchen countertops / kitchenware, toilets / bathrooms, water treatment equipment, livestock breeding sites, etc., common acrylic coatings do not have antibacterial properties or have insufficient antibacterial properties, making it impossible for the environment to meet the antibacterial requirements.

[0005] In summary, it is necessary to develop a new technical solution to solve the deficiencies in the existing technology. Summary of the Invention

[0006] The present invention provides a highly stable antimicrobial acrylic coating composition and a method for preparing the same. The highly stable antimicrobial acrylic coating composition is prepared using a modified acrylic resin, an epoxy resin, a silane polymer, a filler, an additive, and a solvent as raw materials. The modified acrylic resin is obtained by free radical polymerization of an acrylic acid ester of N-phenylmaleimide, butyl acrylate, zinc acrylate, and silica coupled with a fluoroalkyl chain. The highly stable antimicrobial acrylic coating composition exhibits excellent stability, antimicrobial properties, and other comprehensive properties, and has promising application prospects.

[0007] The object of the present invention is to provide a highly stable antibacterial acrylic coating composition, which comprises the following components in parts by weight: 40-50 parts of modified acrylic resin 10-20 parts epoxy resin Silane polymer 5-10 parts 2-5 parts filler 1-10 parts of additives 20-70 parts of solvent; Wherein, the modified acrylic resin is a product obtained by free radical polymerization of N-phenylmaleimide, butyl acrylate, zinc acrylate, and acrylate of silicon dioxide coupled with a fluoroalkyl chain; The acrylate of silicon dioxide coupled with a fluoroalkyl chain is a product of the reaction between hydroxylated silicon dioxide and 2-fluoroacrylic acid.

[0008] Furthermore, the filler is a filler that has undergone surface hydroxylation treatment.

[0009] Furthermore, the auxiliary agent is selected from one or more of a dispersant, a defoaming agent, a leveling agent, an emulsifier, a thickener, a curing agent, a film-forming agent, an antioxidant and a photoinitiator.

[0010] Another object of the present invention is to provide a method for preparing the above-mentioned highly stable antibacterial acrylic coating composition, the method for preparing the highly stable antibacterial acrylic coating composition comprising the following steps: S1, hydroxylating silicon dioxide to obtain hydroxylated silicon dioxide; S2, blending the hydroxylated silica and 2-fluoroacrylic acid, and reacting them by ultrasonic heating to obtain an acrylic acid ester of silica coupled with a fluoroalkyl chain; S3, blending the acrylate of silica coupled with a fluoroalkyl chain, N-phenylmaleimide, butyl acrylate, zinc acrylate, and an initiator, heating and stirring to react, to obtain a modified acrylic resin; S4, mixing silane and acid catalyst, heating and stirring to react, to obtain a silane polymer; S5. Blending and stirring the modified acrylic resin, silane polymer and other components to obtain a high-stability antibacterial acrylic coating composition.

[0011] Furthermore, in step S2, the mass ratio of the hydroxylated silica to 2-fluoroacrylic acid is 1:(2-5).

[0012] Furthermore, in step S2, the temperature of the ultrasonic heating reaction is 70-90°C.

[0013] Furthermore, in step S3, the mass ratio of the acrylate of the silica coupled with a fluoroalkyl chain, N-phenylmaleimide, butyl acrylate, and zinc acrylate is 30:(4-8):(10-14):(1-5).

[0014] Furthermore, in step S3, the temperature of the heating and stirring reaction is 80-100°C.

[0015] Furthermore, in step S4, the temperature of the heating and stirring reaction is 50-70°C.

[0016] The present invention has the following beneficial effects: The highly stable antimicrobial acrylic coating composition of the present invention is prepared using modified acrylic resin, epoxy resin, silane polymer, filler, additive, and solvent as raw materials. The modified acrylic resin is prepared by first grafting 2-fluoroacrylic acid with hydroxylated silica to obtain an acrylic ester of silica coupled with a fluoroalkyl chain, and then subjecting the acrylic ester of silica coupled with a fluoroalkyl chain, N-phenylmaleimide, butyl acrylate, and zinc acrylate to free radical polymerization. The modified acrylic resin introduces a fluorine-containing group through 2-fluoroacrylic acid. The C-F bond has a high bond energy and is not easily destroyed by heat, light or chemical reagents. It also has strong intermolecular forces, thereby improving the stability of the coating composition. Moreover, the introduced N-phenylmaleimide restricts the movement of the resin polymer chain, increases steric hindrance, and thus further improves the stability of the coating composition. In addition, the introduced N-phenylmaleimide can also interact with the sulfur groups in cell membrane proteins, change the conformation, and cause the cytoplasmic membrane to rupture, thereby killing the microorganisms. Finally, the modified acrylic resin also enhances the compatibility of the various components, facilitates the uniform dispersion of different components, avoids aggregation, and enables the components to produce a synergistic effect, thereby improving the overall performance of the coating composition. DETAILED DESCRIPTION

[0017] In order to more clearly illustrate the technical solutions of the present invention, the following examples are given. Unless otherwise stated, the raw materials, reactions and post-processing methods mentioned in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0018] The terms "preferred," "preferably," "more preferred," and the like, used herein, refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

[0019] It should be understood that, except in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present invention.

[0020] The examples of the present invention use the following raw materials: Zinc acrylate was purchased from Jiangsu Leien Environmental Protection Technology Co., Ltd. Dibenzoyl peroxide is the initiator; 2-Fluoroacrylic acid, CAS No. 430-99-9, was purchased from Shandong Zhishang Chemical Co., Ltd.; Methyl silicate is a silane; 15wt% hydrochloric acid as acid catalyst; Epoxy resin was E44 bisphenol A epoxy resin purchased from Guangzhou Rongsheng Chemical Co., Ltd. The additives were photoinitiator Irgacure 2959, curing agent MHG-80B, hydroxyethyl cellulose ether (Dow), and film-forming aid propylene glycol butyl ether in a mass ratio of 1:1:1:1; The solvent is butyl acetate; The filler in the embodiment is hydroxylated silica, and the preparation method of the hydroxylated silica comprises the following steps: mixing silica and glucose in a mass ratio of 1:5 and subjecting the mixture to ball milling (ball-to-material ratio 6:1), washing, centrifuging, and drying to obtain hydroxylated silica.

[0021] Example 1 A high-stability antibacterial acrylic coating composition, comprising the following components in parts by weight: 50 parts of modified acrylic resin 20 parts epoxy resin 10 parts of silane polymer 5 parts filler 10 parts of additives 70 parts of solvent; The preparation method of the high-stability antibacterial acrylic coating composition comprises the following steps: S1. Add silica to a mixture of concentrated sulfuric acid and 30 wt% hydrogen peroxide (the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 7:3), heat to 70°C, react for 1 hour, filter, wash, and dry to obtain hydroxylated silica; S2, blending the hydroxylated silica and 2-fluoroacrylic acid in a mass ratio of 1:3, ultrasonically heating to 80° C. for 2 h, washing, and drying to obtain an acrylate of silica coupled with a fluoroalkyl chain; S3, blending the acrylate of silica coupled with a fluoroalkyl chain, N-phenylmaleimide, N,N-dimethylformamide, butyl acrylate, zinc acrylate, dibenzoyl peroxide, xylene, and n-butanol in a mass ratio of 30:6:15:12:3:1:20:10, heating to 90° C. and stirring for reaction for 5 h, removing the organic solvent, and drying to obtain a modified acrylic resin; S4. Methyl silicate was added to ethanol as a solvent, and then deionized water (methyl silicate:deionized water = 1:1, n / n) was added with stirring. The pH was adjusted to 4 with 15 wt % hydrochloric acid. The mixture was heated to 60° C. and stirred for 4 h. The solvent was removed by distillation under reduced pressure to obtain a silane polymer. S5. Blending and stirring the modified acrylic resin, silane polymer, epoxy resin, filler, additive, and solvent to obtain a high-stability antibacterial acrylic coating composition.

[0022] Example 2 A high-stability antibacterial acrylic coating composition, comprising the following components in parts by weight: 48 parts of modified acrylic resin 20 parts epoxy resin 10 parts of silane polymer 5 parts filler 10 parts of additives 70 parts of solvent; The preparation method of the high-stability antibacterial acrylic coating composition comprises the following steps: S1. Add silica to a mixture of concentrated sulfuric acid and 30 wt% hydrogen peroxide (the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 7:3), heat to 70°C, react for 1 hour, filter, wash, and dry to obtain hydroxylated silica; S2, blending the hydroxylated silica and 2-fluoroacrylic acid in a mass ratio of 1:3, ultrasonically heating to 85° C. for 2 h, washing, and drying to obtain an acrylate of silica coupled with a fluoroalkyl chain; S3, blending the acrylate of silica coupled with a fluoroalkyl chain, N-phenylmaleimide, N,N-dimethylformamide, butyl acrylate, zinc acrylate, dibenzoyl peroxide, xylene, and n-butanol in a mass ratio of 30:6:15:12:3:1:20:10, heating to 90° C. and stirring for reaction for 5 h, removing the organic solvent, and drying to obtain a modified acrylic resin; S4. Methyl silicate was added to ethanol as a solvent, and then deionized water (methyl silicate:deionized water = 1:1, n / n) was added with stirring. The pH was adjusted to 4 with 15 wt % hydrochloric acid. The mixture was heated to 60° C. and stirred for 4 h. The solvent was removed by distillation under reduced pressure to obtain a silane polymer. S5. Blending and stirring the modified acrylic resin, silane polymer, epoxy resin, filler, additive, and solvent to obtain a high-stability antibacterial acrylic coating composition.

[0023] Example 3 A high-stability antibacterial acrylic coating composition, comprising the following components in parts by weight: 50 parts of modified acrylic resin 17 parts epoxy resin 10 parts of silane polymer 5 parts filler 10 parts of additives 70 parts of solvent; The preparation method of the high-stability antibacterial acrylic coating composition comprises the following steps: S1. Add silica to a mixture of concentrated sulfuric acid and 30 wt% hydrogen peroxide (the mass ratio of concentrated sulfuric acid to hydrogen peroxide is 7:3), heat to 70°C, react for 1 hour, filter, wash, and dry to obtain hydroxylated silica; S2, blending the hydroxylated silica and 2-fluoroacrylic acid in a mass ratio of 1:3, ultrasonically heating to 80° C. for 2 h, washing, and drying to obtain an acrylate of silica coupled with a fluoroalkyl chain; S3, blending the acrylate of the silica coupled with a fluoroalkyl chain, N-phenylmaleimide, N,N-dimethylformamide, butyl acrylate, zinc acrylate, dibenzoyl peroxide, xylene, and n-butanol in a mass ratio of 30:6:15:12:3:1:20:10, heating to 95° C. and stirring for reaction for 5 h, removing the organic solvent, and drying to obtain a modified acrylic resin; S4. Methyl silicate was added to ethanol as a solvent, and then deionized water (methyl silicate:deionized water = 1:1, n / n) was added with stirring. The pH was adjusted to 4 with 15 wt % hydrochloric acid. The mixture was heated to 60° C. and stirred for 4 h. The solvent was removed by distillation under reduced pressure to obtain a silane polymer. S5. Blending and stirring the modified acrylic resin, silane polymer, epoxy resin, filler, additive, and solvent to obtain a high-stability antibacterial acrylic coating composition.

[0024] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that N-phenylmaleimide in step S3 is deleted, and the remaining components and preparation method are the same as those in Example 1.

[0025] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that 2-fluoroacrylic acid in step S2 is replaced by acrylic acid, and the remaining components and preparation method are the same as those in Example 1.

[0026] Test Example 1 Performance tests were performed on the high-stability antibacterial acrylic coating compositions of Examples 1-3 and Comparative Examples 1-2.

[0027] Test method: After the surface of the tinplate sheet was polished and cleaned, the sample coatings of Examples 1-3 and Comparative Examples 1-2 were coated respectively, cured at 60° C. for 5 h, and then irradiated with ultraviolet light to obtain coating samples.

[0028] Heat resistance: The coating samples were placed in a thermogravimetric analyzer (TGA) for testing in a temperature range of 30-300°C in a nitrogen environment at a heating rate of 10°C / min.

[0029] Adhesion: Tested in accordance with GB / T 9286 standard.

[0030] Antibacterial property: The coating samples were tested for antibacterial activity against Staphylococcus aureus in accordance with the national standard GB / T 21866-2008, Determination of antibacterial activity and antibacterial effect of antibacterial coatings (paint films).

[0031] Weather resistance: tested in accordance with GB / T 14522 standard.

[0032] Acid resistance: The coating samples were immersed in 10 wt% HCl for acid corrosion test.

[0033] Alkali resistance: The coating samples were immersed in 10wt% NaOH for alkali corrosion resistance test.

[0034] The test results are shown in Table 1.

[0035] Table 1 Performance test results of high stability antibacterial acrylic coating composition project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 <![CDATA[Heat resistance / T 10% (°C)]]> 167 165 166 150 155 Adhesion Level 0 Level 0 Level 0 Level 1 Level 1 Antibacterial properties 99.3 99.5 99.4 88.9 99.2 Weather resistance / 4000h No abnormalities No abnormalities No abnormalities A small amount of bubbles A small amount of bubbles Acid resistance / 96h No abnormalities No abnormalities No abnormalities A few rust spots A few rust spots Alkali resistance / 96h No abnormalities No abnormalities No abnormalities A few rust spots A few rust spots As can be seen from Table 1, the various properties of Examples 1-3 are better than those of Comparative Examples 1-2. This is because Comparative Example 1 does not add N-phenylmaleimide, which significantly reduces the heat resistance and antibacterial properties of the coating, and weakens the synergistic effect between different components, resulting in a certain degree of reduction in other properties. Comparative Example 2 replaces 2-fluoroacrylic acid with acrylic acid, and does not introduce a fluorine-containing group, which reduces the heat resistance of the coating, and reduces the synergistic effect of the components, resulting in varying degrees of reduction in other properties.

[0036] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0037] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A high-stability antibacterial acrylic coating composition, characterized in that: The high-stability antibacterial acrylic coating composition comprises the following components in parts by mass: 40-50 parts of modified acrylic resin 10-20 parts epoxy resin Silane polymer 5-10 parts 2-5 parts filler 1-10 parts of additives 20-70 parts of solvent; Wherein, the modified acrylic resin is a product obtained by free radical polymerization of N-phenylmaleimide, butyl acrylate, zinc acrylate, and acrylate of silicon dioxide coupled with a fluoroalkyl chain; The acrylate of silicon dioxide coupled with a fluoroalkyl chain is a product of the reaction between hydroxylated silicon dioxide and 2-fluoroacrylic acid.

2. The high-stability antibacterial acrylic coating composition according to claim 1, wherein The filler is a filler that has undergone surface hydroxylation treatment.

3. The high-stability antibacterial acrylic coating composition according to claim 1, wherein The auxiliary agent is selected from one or more of a dispersant, a defoamer, a leveling agent, an emulsifier, a thickener, a curing agent, a film-forming agent, an antioxidant and a photoinitiator.

4. The method for preparing the high-stability antimicrobial acrylic coating composition according to any one of claims 1 to 3, characterized in that: The preparation method of the high-stability antibacterial acrylic coating composition comprises the following steps: S1, hydroxylating silicon dioxide to obtain hydroxylated silicon dioxide; S2, blending the hydroxylated silica and 2-fluoroacrylic acid, and reacting them by ultrasonic heating to obtain an acrylic acid ester of silica coupled with a fluoroalkyl chain; S3, blending the acrylate of silica coupled with a fluoroalkyl chain, N-phenylmaleimide, butyl acrylate, zinc acrylate, and an initiator, heating and stirring to react, to obtain a modified acrylic resin; S4, mixing silane and acid catalyst, heating and stirring to react, to obtain a silane polymer; S5. Blending and stirring the modified acrylic resin, silane polymer and other components to obtain a high-stability antibacterial acrylic coating composition.

5. The method for preparing the high-stability antibacterial acrylic coating composition according to claim 4, wherein: In step S2, the mass ratio of the hydroxylated silica to 2-fluoroacrylic acid is 1:(2-5).

6. The method for preparing the high-stability antibacterial acrylic coating composition according to claim 4, wherein: In step S2, the temperature of the ultrasonic heating reaction is 70-90°C.

7. The method for preparing the high-stability antibacterial acrylic coating composition according to claim 4, wherein: In step S3, the mass ratio of the acrylate of the silica coupled with a fluoroalkyl chain, N-phenylmaleimide, butyl acrylate, and zinc acrylate is 30:(4-8):(10-14):(1-5).

8. The method for preparing the high-stability antibacterial acrylic coating composition according to claim 4, wherein: In step S3, the temperature of the heating and stirring reaction is 80-100°C.

9. The method for preparing the high-stability antimicrobial acrylic coating composition according to claim 4, wherein: In step S4, the temperature of the heating and stirring reaction is 50-70°C.