Long-acting antibacterial antifouling acrylic resin modified coating material and preparation method and application thereof

Abstract

This invention provides a long-lasting antibacterial and antifouling acrylic resin modified coating material, its preparation method, and its applications. The preparation method involves adding a modified phenolic antibacterial agent containing an acrylate structure to an acrylate prepolymer, copolymerizing it with the acrylic resin prepolymer, and then introducing a perfluoropolyether structure to increase hydrophobicity, antifouling properties, and anti-graffiti properties, resulting in a coating with excellent antibacterial and antifouling performance. This invention, by adding KH570 to the coating to create a siloxane-containing structure, not only achieves high bonding strength with plastic products but can also be applied to glass surfaces, broadening its application range. The coating prepared by this invention exhibits excellent broad-spectrum antibacterial properties, high transparency, and wear resistance, while also being antifouling and easy to clean. It also shows good adhesion to substrates such as glass and ceramics, meeting the needs of various application scenarios.

Description

Technical Field

[0001] This invention relates to the field of antibacterial and antifouling technology, and in particular to a long-lasting antibacterial and antifouling acrylic resin modified coating material, its preparation method, and its application. Background Technology

[0002] With social development and progress, people are paying more attention to antibacterial protection. Antibacterial agents are usually applied by spraying or coating with alcohol, sodium hypochlorite, etc. However, the durability of these products is poor, and the coating needs to be reinforced frequently to achieve the antibacterial effect, which greatly increases labor costs.

[0003] Commercially available antibacterial agents generally have short-lasting effects and are easily wiped off, failing to meet the needs of applications requiring both antibacterial and hydrophobic / fouling resistance. For example, mobile phone screens need to be antibacterial and fingerprint-resistant, while handles need to be both clean and antibacterial. As people increasingly value self-protection against bacteria, current products on the market suffer from limited functionality, inability to adhere permanently to substrates, and easy wiping. Therefore, developing long-lasting, multifunctional antibacterial agents that meet the needs of various scenarios has become an urgent problem to solve. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a long-lasting antibacterial and antifouling acrylic resin modified coating material, its preparation method, and its applications. This invention obtains an acrylic resin modified coating by copolymerizing acrylate-containing antibacterial units, acrylate-containing hydrophobic units, a coupling agent, an initiator, and acrylic resin in a specific ratio. The coating prepared by this invention exhibits excellent broad-spectrum antibacterial properties, high transparency, and wear resistance, while also being antifouling and easy to clean. It also demonstrates good adhesion and wear resistance on substrates such as glass and ceramics, meeting the application requirements of various scenarios.

[0005] The technical solution of the present invention is as follows:

[0006] The first aspect of this invention provides a long-lasting antibacterial and antifouling acrylic resin modified coating material, comprising the following raw material components by weight:

[0007] 0.5 to 2 parts of antibacterial unit containing acrylate; 5 to 20 parts of hydrophobic unit containing acrylate; 0.5 to 2 parts of coupling agent; 35 to 50 parts of multifunctional polyurethane acrylate; 30 to 40 parts of reactive diluent; 0.1 to 0.3 parts of initiator; 10 to 30 parts of organic solvent.

[0008] In some embodiments, the general structural formula of the acrylate-containing antimicrobial unit is shown in formula (Ⅰ):

[0009]

[0010] The R is selected from any of the following groups:

[0011]

[0012] In some embodiments, the general structural formula of the acrylate-containing hydrophobic unit is shown in formula (II) below:

[0013]

[0014] In the formula:

[0015] The chemical structural formula of the Rf is F-(CF2). d -(OC3F6) e -(OC2F4) f -(OCF2) g -O-(CF2) h CF2-

[0016] Where e, f, and g are each represented independently as integers between 0 and 100, and the sum of f and g is not less than 1, while d and h are both integers between 0 and 30;

[0017] The order and number of repeating units with e, f, and g enclosed in parentheses are arbitrary in the formula; that is, the structural formula of Rf also includes:

[0018] F-(CF2) d -(OC3F6) e -(OCF2) g -(OC2F4) f -O-(CF2) h CF2-、

[0019] F-(CF2) d -(OC2F4) f -(OC3F6) e -(OCF2) g -O-(CF2) h CF2-、

[0020] F-(CF2) d -(OC2F4) f -(OCF2) g -(OC3F6) e -O-(CF2) h CF2-、

[0021] F-(CF2) d -(OCF2) g -(OC2F4) f -(OC3F6) e-O-(CF2) h CF2- or

[0022] F-(CF2) d -(OCF2) g -(OC3F6) e -(OC2F4) f -O-(CF2) h CF2-.

[0023] In some embodiments, the coupling agent is a silane coupling agent KH570.

[0024] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone (1173), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexylphenyl ketone (184), and 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone (907). Preferably, the initiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0025] In some embodiments, the multifunctional polyurethane acrylate refers to a polyurethane acrylate oligomer, and the functionality of the multifunctional polyurethane acrylate includes 4 to 6 functions; preferably, the multifunctional polyurethane acrylate is 230A2 polyurethane acrylate from Shanghai Guangyi Chemical Co., Ltd.

[0026] In some embodiments, the reactive diluent includes one or more of methyl acrylate, ethyl acrylate, and methyl methacrylate, preferably methyl methacrylate.

[0027] In some embodiments, the organic solvent includes one or both of ethyl acetate and n-butyl acetate, preferably n-butyl acetate.

[0028] A second aspect of the present invention provides a method for preparing the long-lasting antibacterial and antifouling acrylic resin modified coating material described in the first aspect, comprising the following steps:

[0029] S1: Preparation of antibacterial units containing acrylate;

[0030] S2: Preparation of hydrophobic units containing acrylates;

[0031] S3: By weight, mix 0.5 to 2 parts of antibacterial unit containing acrylate, 5 to 20 parts of hydrophobic unit containing acrylate, 0.5 to 2 parts of coupling agent, 35 to 50 parts of multifunctional polyurethane acrylate, 30 to 40 parts of reactive diluent, 0.1 to 0.3 parts of initiator, and 10 to 30 parts of organic solvent, and stir at 25 to 50°C for 15 to 60 minutes to obtain a long-lasting antibacterial and antifouling acrylic resin modified coating material.

[0032] In some embodiments, the preparation method of the acrylate-containing antibacterial unit is as follows: a phenolic antibacterial agent is mixed evenly with a solvent and an acid-binding agent, then acryloyl chloride is added dropwise in an ice bath, and the mixture is reacted at 25-50°C for 2-4 hours. After removing excess solvent by rotary evaporation, the mixture is purified by extraction, dried, filtered, and the solvent is removed by rotary evaporation to obtain the acrylate-containing antibacterial unit.

[0033] In some embodiments, the phenolic antibacterial agent includes one or more of 5-chloro-2-(2,4-dichlorophenoxy)phenol, p-chloro-m-xylenol, 3-methyl-4-isopropylphenol, 5-isopropyl-2-methylphenol, and 2,4-dichloro-3,5-dimethylphenol; preferably, the phenolic antibacterial agent is 5-chloro-2-(2,4-dichlorophenoxy)phenol.

[0034] In some embodiments, the acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate, preferably potassium carbonate.

[0035] In some embodiments, the solvent includes one or more of dichloromethane, tetrahydrofuran, and xylene, preferably dichloromethane.

[0036] In some embodiments, the mass-to-volume ratio of the phenolic antibacterial agent to the solvent is 10g:15ml to 10g:30ml; the mass ratio of the phenolic antibacterial agent to acryloyl chloride is 10:4 to 10:9; and the mass ratio of the acid-binding agent to acryloyl chloride is 10:7 to 10:14.

[0037] In some embodiments, the preparation method of the acrylate-containing hydrophobic unit is as follows: a perfluoropolyether alcohol is mixed evenly with a fluorinated solvent and an acid-binding agent, acryloyl chloride is added dropwise in an ice bath and reacted at 25-50°C. After the reaction is completed, the mixture is first extracted and then rotary evaporated to remove excess solvent. Then, it is extracted with methanol and SV70 and rotary evaporated to remove excess solvent to obtain the acrylate-containing hydrophobic unit.

[0038] In some embodiments, the perfluoropolyether alcohol is a Z-type perfluoropolyether alcohol.

[0039] In some embodiments, the fluorinated solvent includes one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecylfluorohexyl methyl ether, hydrofluoroether, fluorocarbons, and m-difluorotoluene.

[0040] In some embodiments, the acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate, preferably potassium carbonate.

[0041] In some embodiments, the mass-to-volume ratio of the perfluoropolyether alcohol to the fluorinated solvent is 10g:15ml to 10g:30ml; the mass ratio of the perfluoropolyether alcohol to acryloyl chloride is 10:0.4 to 10:1; and the mass ratio of the perfluoropolyether alcohol to the acid-binding agent is 10:0.7 to 10:1.

[0042] The third aspect of the present invention provides an application of a long-lasting antibacterial and antifouling acrylic resin modified coating material prepared by the method described in the second aspect above, or the long-lasting antibacterial and antifouling acrylic resin modified coating material described in the first aspect above, wherein the long-lasting antibacterial and antifouling acrylic resin modified coating material is used to prepare a long-lasting antibacterial and antifouling acrylic resin modified coating.

[0043] In some embodiments, the preparation method of the long-lasting antibacterial and antifouling acrylic resin modified coating is as follows: the long-lasting antibacterial and antifouling acrylic resin modified coating material prepared above is sprayed onto the surface of a pretreated substrate, dried and cured to obtain a modified coating with a thickness of 5 to 20 μm.

[0044] In some embodiments, the pretreated substrate refers to a substrate surface subjected to corona treatment for 30 seconds to 1 minute.

[0045] The beneficial technical effects of this invention are as follows:

[0046] This invention provides a long-lasting antibacterial and antifouling acrylic resin modified coating. By introducing perfluoropolyether, the antifouling performance of the acrylic resin is greatly improved, achieving a static water droplet angle of approximately 103°, effectively preventing contaminant adhesion and providing easy cleaning. The introduction of acrylate-containing antibacterial units gives the modified coating excellent broad-spectrum antibacterial properties, achieving an inhibition rate of 98.2% against Staphylococcus aureus and 98.1% against Escherichia coli.

[0047] Due to the low surface tension of the perfluoropolyether group, the introduction of this group can not only play a role in hydrophobicity and antifouling, but also in resisting bioadhesion. This not only reduces the amount of antibacterial unit used, but also achieves excellent antibacterial effect. At the same time, the reduction in the amount of antibacterial unit used also reduces the impact on the hardness and transparency of the coating after film formation.

[0048] The long-lasting antibacterial and antifouling acrylic resin modified coating prepared by this invention has a wide range of applications. It can be applied not only to plastics, but also to substrates such as glass and ceramics to form a stable, wear-resistant, and transparent coating. Attached Figure Description

[0049] Figure 1 The above is the 1H NMR spectrum of the acrylate-containing hydrophobic unit prepared in Example 1 of this invention. Detailed Implementation

[0050] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0051] The first aspect of this invention provides a long-lasting antibacterial and antifouling acrylic resin modified coating material, comprising the following raw material components by weight:

[0052] 0.5 to 2 parts of antibacterial unit containing acrylate; 5 to 20 parts of hydrophobic unit containing acrylate; 0.5 to 2 parts of coupling agent; 35 to 50 parts of multifunctional polyurethane acrylate; 30 to 40 parts of reactive diluent; 0.1 to 0.3 parts of initiator; 10 to 30 parts of organic solvent.

[0053] In some embodiments, the acrylate-containing antimicrobial unit is prepared by reacting acryloyl chloride with a phenolic antimicrobial agent.

[0054] In some embodiments, the phenolic antibacterial agent includes one or more of 5-chloro-2-(2,4-dichlorophenoxy)phenol, p-chloro-m-xylenol, 3-methyl-4-isopropylphenol, 5-isopropyl-2-methylphenol, and 2,4-dichloro-3,5-dimethylphenol. Preferably, the phenolic antibacterial agent is 5-chloro-2-(2,4-dichlorophenoxy)phenol.

[0055] In this invention, phenolic antibacterial agents possess broad-spectrum and highly efficient antibacterial properties. Further, through reaction with acryloyl chloride, an acrylate-containing antibacterial unit is obtained. Firstly, this gives the coating excellent broad-spectrum antibacterial properties, exhibiting killing and inhibitory effects against Gram-positive bacteria, Gram-negative bacteria, yeast, and viruses. Secondly, it improves the chemical properties, solubility, and stability of the phenolic antibacterial agent, enhancing its antibacterial durability. Simultaneously, the antibacterial unit synergistically interacts with perfluoropolyether substances to enhance antibacterial adhesion and bactericidal effects.

[0056] In some embodiments, the general structural formula of the acrylate-containing antimicrobial unit is shown in formula (Ⅰ):

[0057]

[0058] The R is selected from any of the following groups:

[0059]

[0060] In some embodiments, the acrylate-containing hydrophobic unit is obtained by reacting acryloyl chloride with perfluoropolyether alcohol.

[0061] In some embodiments, the perfluoropolyether comprises Z-type perfluoropolyether alcohol, CAS number 90317-77-4.

[0062] In this invention, the Z-type perfluorinated polyether alcohol is polymerized from perfluorinated compound monomers. It has low surface energy and high stability, and has a strong repellency to water and oil. It can effectively prevent various organic and inorganic substances from adsorbing and adhering to it. At the same time, this type of polymer compound has excellent slip properties on the substrate, which can provide a better user experience.

[0063] It is understood that the acrylate-containing hydrophobic unit of this invention is obtained by modifying perfluoropolyether alcohol, giving the coating the characteristics of perfluoropolyether polymers, thereby achieving effective hydrophobicity and anti-fingerprint properties. Furthermore, through synergy with antibacterial agents and silane coupling agents, the antibacterial properties, adhesion, and durability of the coating are further improved.

[0064] In some embodiments, the general structural formula of the acrylate-containing hydrophobic unit is shown in formula (II) below:

[0065]

[0066] In the formula:

[0067] The chemical structural formula of the Rf is F-(CF2). d -(OC3F6) e -(OC2F4) f -(OCF2) g -O-(CF2) h CF2-

[0068] Where e, f, and g are each represented independently as integers between 0 and 100, and the sum of f and g is not less than 1, while d and h are both integers between 0 and 30;

[0069] The order and number of repeating units with e, f, and g enclosed in parentheses are arbitrary in the formula; that is, the structural formula of Rf also includes:

[0070] F-(CF2) d -(OC3F6) e -(OCF2) g -(OC2F4) f -O-(CF2) h CF2-、

[0071] F-(CF2) d -(OC2F4) f -(OC3F6) e -(OCF2) g -O-(CF2) h CF2-、

[0072] F-(CF2) d -(OC2F4) f -(OCF2) g -(OC3F6) e -O-(CF2) h CF2-、

[0073] F-(CF2) d -(OCF2) g -(OC2F4) f -(OC3F6) e -O-(CF2) h CF2- or

[0074] F-(CF2) d -(OCF2) g -(OC3F6) e -(OC2F4) f -O-(CF2) h CF2-.

[0075] In one embodiment of this application, the structure of the acrylate-containing hydrophobic unit is: CF3-(OC2F4). m -(OCF2) n -O-CF2-CH2-OC(O)-CH=CH2 Equation II, where m and n are independently represented as integers between 0 and 100.

[0076] In this application, m can be one of d, e, f, g, h; n can be one of d, e, f, g, h.

[0077] In some embodiments, the coupling agent is a silane coupling agent KH570.

[0078] In this invention, the silane coupling agent contains methacryloxy groups, which can copolymerize with acrylic monomers to connect the glass and the acrylic resin layer, thereby increasing the adhesion of the acrylic resin to the glass substrate.

[0079] In some embodiments, the initiator includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone (1173), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1-hydroxycyclohexylphenyl ketone (184), and 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone (907). Preferably, the initiator is 2-hydroxy-2-methyl-1-phenylpropanone.

[0080] In some embodiments, the multifunctional polyurethane acrylate refers to a polyurethane acrylate oligomer, and the functionality of the multifunctional polyurethane acrylate includes 4 to 6 functions; preferably, the multifunctional polyurethane acrylate is 230A2 polyurethane acrylate from Shanghai Guangyi Chemical Co., Ltd.

[0081] In this invention, multifunctional polyurethane acrylates can crosslink and cure with functional agents containing acrylate functional groups through chemical reactions, further improving the coating's antifouling, antibacterial, adhesion, abrasion resistance, and weather resistance. The 230A2 polyurethane acrylate used has a more suitable functional ratio structure compared to other polyurethane acrylates, forming a better film structure, and is inexpensive and readily available, making it suitable for the large-scale application of the functional coatings of this invention.

[0082] In some embodiments, the reactive diluent includes one or more of methyl acrylate, ethyl acrylate, and methyl methacrylate, preferably methyl methacrylate.

[0083] In some embodiments, the organic solvent includes one or both of ethyl acetate and n-butyl acetate, preferably n-butyl acetate.

[0084] This invention also protects a method for preparing the long-lasting antibacterial and antifouling acrylic resin modified coating material described in the first aspect above, comprising the following steps:

[0085] S1: Preparation of antibacterial units containing acrylate;

[0086] S2: Preparation of hydrophobic units containing acrylates;

[0087] S3: By weight, mix 0.5 to 2 parts of antibacterial unit containing acrylate, 5 to 20 parts of hydrophobic unit containing acrylate, 0.5 to 2 parts of coupling agent, 35 to 50 parts of multifunctional polyurethane acrylate, 30 to 40 parts of reactive diluent, 0.1 to 0.3 parts of initiator, and 10 to 30 parts of organic solvent, and stir at 25 to 50°C for 15 to 60 minutes to obtain a long-lasting antibacterial and antifouling acrylic resin modified coating material.

[0088] In this invention, substrate pretreatment can improve surface energy and adhesion, as well as improve the cleanliness of the substrate surface, thus preventing the coating from not bonding firmly to the substrate.

[0089] In some embodiments, the preparation method of the acrylate-containing antibacterial unit is as follows: a phenolic antibacterial agent is mixed evenly with a solvent and an acid-binding agent, then acryloyl chloride is added dropwise in an ice bath, and the mixture is reacted at 25-50°C for 2-4 hours. After removing excess solvent by rotary evaporation, the mixture is purified by extraction, dried, filtered, and the solvent is removed by rotary evaporation to obtain the acrylate-containing antibacterial unit.

[0090] In some embodiments, the acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate, preferably potassium carbonate.

[0091] In some embodiments, the solvent includes one or more of dichloromethane, tetrahydrofuran, and xylene, preferably dichloromethane.

[0092] In some embodiments, the mass-to-volume ratio of the phenolic antibacterial agent to the solvent is 10g:15mL to 10g:30mL; the mass ratio of the phenolic antibacterial agent to acryloyl chloride is 10:4 to 10:9; and the mass ratio of the acid-binding agent to acryloyl chloride is 10:7 to 10:14. In some embodiments, the preparation method of the acrylate-containing hydrophobic unit is as follows: A perfluoropolyether alcohol is mixed uniformly with a fluorinated solvent and an acid-binding agent. Acryloyl chloride is added dropwise in an ice bath, and the reaction is carried out at 25–50°C. After the reaction is complete, the mixture is first extracted, then rotary evaporated to remove excess solvent. The mixture is then extracted again with methanol and SV70, and rotary evaporated to remove excess solvent, yielding the acrylate-containing hydrophobic unit.

[0093] In some embodiments, the perfluoropolyether alcohol is a Z-type perfluoropolyether alcohol.

[0094] In some embodiments, the fluorinated solvent includes one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecylfluorohexyl methyl ether, hydrofluoroether, fluorocarbons, and m-difluorotoluene.

[0095] In some embodiments, the acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate, preferably potassium carbonate.

[0096] In some embodiments, the mass-to-volume ratio of the perfluoropolyether alcohol to the fluorinated solvent is 10g:15mL to 10g:30mL; the mass ratio of the perfluoropolyether alcohol to acryloyl chloride is 10:0.4 to 10:1; and the mass ratio of the perfluoropolyether alcohol to the acid-binding agent is 10:0.7 to 10:1.

[0097] The third aspect of the present invention provides an application of a long-lasting antibacterial and antifouling acrylic resin modified coating material prepared by the method described in the second aspect above, or the long-lasting antibacterial and antifouling acrylic resin modified coating material described in the first aspect above, wherein the long-lasting antibacterial and antifouling acrylic resin modified coating material is used to prepare a long-lasting antibacterial and antifouling acrylic resin modified coating.

[0098] In some embodiments, the preparation method of the long-lasting antibacterial and antifouling acrylic resin modified coating is as follows: the long-lasting antibacterial and antifouling acrylic resin modified coating material prepared above is sprayed onto the surface of a pretreated substrate, dried and cured to obtain a modified coating with a thickness of 1 to 20 μm.

[0099] In some embodiments, the pretreated substrate refers to a substrate surface subjected to corona treatment for 30 seconds to 1 minute.

[0100] The present invention will be further illustrated below through examples and comparative examples.

[0101] Example 1

[0102] An antibacterial and antifouling acrylate modified coating material and coating, the preparation method of which includes the following steps:

[0103] S1 prepares an acrylate-containing antibacterial unit:

[0104] 10g of 5-chloro-2-(2,4-dichlorophenoxy)phenol, 7.4g of potassium carbonate, and 20ml of dichloromethane were mixed thoroughly. Then, 4.7g of acryloyl chloride was added dropwise under ice bath conditions. The mixture was reacted at 30°C for 3 hours. After the reaction was completed, excess solvent was removed by rotary evaporation. The mixture was then extracted with water and dichloromethane. The lower extract was dehydrated with anhydrous magnesium sulfate and filtered. The solvent was removed by rotary evaporation to obtain Formula I, i.e., the antibacterial unit containing acrylate, denoted as antibacterial component A.

[0105]

[0106] S2 is used to prepare hydrophobic units containing acrylates:

[0107] First, mix 10g of perfluoropolyether alcohol (M=2200, CAS No. 90317-77-4), 0.96g of potassium carbonate and 20ml of m-difluoromethylbenzene evenly. Then, add 0.5g of acryloyl chloride dropwise in an ice bath and react at 30℃ for 3 hours. After the reaction is completed, extract with water first, remove the solvent by rotary evaporation of the lower layer, and then extract with methanol and SV70 and rotary evaporation to obtain the following formula II, i.e., the hydrophobic unit containing acrylate, denoted as hydrophobic and antifouling component B.

[0108] CF3-(OC2F4) m -(OCF2) n -O-CF2-CH2-OC(O)-CH=CH2 Formula II

[0109] S3: According to the mass fractions, take 1 part of antibacterial unit A containing acrylate, 10 parts of hydrophobic and antifouling component B containing acrylate, 0.5 parts of KH570, 35 parts of 230A2 polyurethane acrylate, 30 parts of methyl methacrylate, 1 part of 2-hydroxy-2-methyl-1-phenylpropanone, and 20 parts of n-butyl acetate and mix them all. Heat and stir at 50°C for 1 hour under argon protection to obtain antibacterial and antifouling acrylate modified coating material or slurry.

[0110] The glass was corona-treated for 1 minute, then sprayed with a sprayer, baked at 80℃ for 1 minute, and then UV-cured at a curing energy of 800 mJ / cm². 2 Sample 1 containing the coating can then be obtained.

[0111] Example 2

[0112] An antibacterial and antifouling acrylate modified coating material and coating, the preparation method of which includes the following steps:

[0113] S1 prepares an acrylate-containing antibacterial unit:

[0114] First, mix 10g of p-chloro-meta-xylenol, 13.25g of potassium carbonate and 20ml of dichloromethane evenly. Then, add 8.7g of acryloyl chloride dropwise under ice bath conditions. React at 30℃ for 3 hours. After the reaction is complete, remove excess solvent by rotary evaporation. Extract with water and dichloromethane. Remove water from the lower extract with anhydrous magnesium sulfate and filter. Remove solvent by rotary evaporation to obtain Formula III, i.e., hydrophobic unit containing acrylate, denoted as antibacterial component A.

[0115]

[0116] S2 is used to prepare hydrophobic units containing acrylates:

[0117] First, 10g of perfluoropolyether alcohol (M=2200, CAS No. 90317-77-4), 0.96g of potassium carbonate and 20ml of m-difluoromethylbenzene were mixed evenly. 0.8g of acryloyl chloride was added dropwise in an ice bath and the mixture was reacted at 30℃ for 3 hours. After the reaction was completed, the mixture was first extracted with water, and the solvent was removed by rotary evaporation of the lower layer. Then, the mixture was extracted with methanol and SV70 and rotary evaporated to obtain Formula II, i.e., the hydrophobic unit containing acrylate, which is denoted as antifouling component B.

[0118] CF3-(OC2F4) m -(OCF2) n -O-CF2-CH2-OC(O)-CH=CH2 Formula II

[0119] S3: Take 1 part of the antibacterial unit containing acrylate, i.e., antibacterial component A, 10 parts of the hydrophobic unit containing acrylate, i.e., antifouling component B, 0.5 parts of KH570, 35 parts of 230A2 polyurethane acrylate, 30 parts of methyl methacrylate, 1 part of 2-hydroxy-2-methyl-1-phenylpropanone, and 20 parts of n-butyl acetate and mix them all together. Heat and stir at 50°C for 1 hour under argon protection to obtain antibacterial and antifouling acrylate modified coating material or slurry.

[0120] The glass was corona-treated for 1 minute, then sprayed with a sprayer, baked at 80℃ for 1 minute, and then UV-cured at a curing energy of 800 mJ / cm². 2 Sample 2 with coating can then be obtained.

[0121] Example 3

[0122] An antibacterial and antifouling acrylate modified coating material and coating, the preparation method of which includes the following steps:

[0123] S1 prepares an acrylate-containing antibacterial unit:

[0124] First, mix 10g of 3-methyl-4-isopropylphenol, 13.8g of potassium carbonate and 20ml of dichloromethane evenly. Then, add 9.0g of acryloyl chloride dropwise under ice bath conditions. React at 30℃ for 3 hours. After the reaction is complete, remove excess solvent by rotary evaporation. Extract with water and dichloromethane. Remove water from the lower extract with anhydrous magnesium sulfate and filter. Remove solvent by rotary evaporation to obtain Formula IV, i.e., hydrophobic unit containing acrylate, denoted as antibacterial component A.

[0125]

[0126] S2 is used to prepare hydrophobic units containing acrylates:

[0127] First, mix 10g of perfluoropolyether alcohol (M=2200, CAS No. 90317-77-4), 0.96g of potassium carbonate and 20ml of m-difluoromethylbenzene evenly. Then, add 0.9g of acryloyl chloride dropwise in an ice bath and react at 30℃ for 3 hours. After the reaction is complete, extract with water first, remove the solvent by rotary evaporation of the lower layer, and then extract with methanol and SV70 and rotary evaporation to obtain Formula II, i.e., the hydrophobic unit containing acrylate, denoted as antifouling component B.

[0128] CF3-(OC2F4) m -(OCF2) n -O-CF2-CH2-OC(O)-CH=CH2 Formula II

[0129] S3: Take 1 part of antifouling component A, 10 parts of antifouling component B, 0.5 parts of KH570, 35 parts of 230A2 polyurethane acrylate, 30 parts of methyl methacrylate, 1 part of 2-hydroxy-2-methyl-1-phenylpropanone, and 20 parts of n-butyl acetate and mix them all. Heat and stir at 50°C for 1 hour under argon protection to obtain antibacterial and antifouling acrylate modified coating material or slurry.

[0130] The glass was corona-treated for 1 minute, then sprayed with a sprayer, baked at 80℃ for 1 minute, and then UV-cured at a curing energy of 800 mJ / cm². 2 Sample 3 containing the coating can then be obtained.

[0131] Example 4

[0132] Similar to Example 1, except that in Example 4, the mass of the antibacterial unit containing acrylate is 0.5 parts.

[0133] The sample preparation method is the same as in Example 1.

[0134] Example 5

[0135] Similar to Example 1, except that in Example 5, the mass of the antibacterial unit containing acrylate is 1.5 parts.

[0136] The sample preparation method is the same as in Example 1.

[0137] Example 6

[0138] Similar to Example 1, except that in Example 6, the mass of the antibacterial unit containing acrylate is 2 parts.

[0139] The sample preparation method is the same as in Example 1.

[0140] Example 7

[0141] Similar to Example 1, except that in Example 7, the mass of KH570 is 1.5 parts.

[0142] The sample preparation method is the same as in Example 1.

[0143] Example 8

[0144] Similar to Example 1, except that in Example 8, the mass of KH570 is 1 part.

[0145] The sample preparation method is the same as in Example 1.

[0146] Example 9

[0147] Similar to Example 1, except that in Example 9, the mass of KH570 is 2 parts.

[0148] The sample preparation method is the same as in Example 1.

[0149] Example 10

[0150] Similar to Example 1, except that in Example 10, the mass of the hydrophobic unit containing acrylate is 5 parts.

[0151] The sample preparation method is the same as in Example 1.

[0152] Example 11

[0153] Similar to Example 1, except that in Example 11, the mass of the hydrophobic unit containing acrylate is 15 parts.

[0154] The sample preparation method is the same as in Example 1.

[0155] Example 12

[0156] Similar to Example 1, except that in Example 12, the mass of the hydrophobic unit containing acrylate is 20 parts.

[0157] The sample preparation method is the same as in Example 1.

[0158] Comparative Example 1

[0159] Similar to Example 1, except that Comparative Example 1 uses K-type perfluoropolyether.

[0160] The synthesized hydrophobic unit II is shown below:

[0161] CF3CF2CF2-O-[CF(CF3)CF2O] m -O-CF(CF3)-CH2-OC(O)-CH=CH2

[0162] The preparation methods for the remaining raw materials and samples are the same as in Example 1.

[0163] Comparative Example 2

[0164] Similar to Example 1, except that the antibacterial unit used in Comparative Example 2 is hexadecyltrimethylammonium chloride.

[0165] Comparative Example 3

[0166] Similar to Example 1, except that the antibacterial unit containing acrylate used in Comparative Example 3 was 0.3 parts.

[0167] Comparative Example 4

[0168] Similar to Example 1, except that the amount of acrylate-containing antibacterial unit used in Comparative Example 4 was 2.5 parts.

[0169] Comparative Example 5

[0170] Similar to Example 1, except that in Comparative Example 5, the amount of acrylate-containing hydrophobic units used was 3 parts.

[0171] Comparative Example 6

[0172] Similar to Example 1, except that 22 parts of the acrylate-containing hydrophobic unit were used in Comparative Example 6.

[0173] Comparative Example 7

[0174] Similar to Example 1, except that Comparative Example 7 uses KH550.

[0175] Comparative Example 8

[0176] Similar to Example 1, except that in Comparative Example 8, the coating was not prepared by corona treatment but by direct spraying.

[0177] Test case

[0178] (1) Antibacterial performance test:

[0179] According to the national standard GB / T4789.2, the antibacterial properties of the coatings prepared in the test examples and comparative examples were evaluated. The bacterial strains selected for the experiment were Escherichia coli and Staphylococcus aureus.

[0180] (2) Antifouling performance test

[0181] The water contact angle performance of the products prepared in the embodiments and comparative examples of the present invention was tested using a water droplet angle tester in accordance with the national standard GBT 24368-2009.

[0182] (3) Adhesion performance test

[0183] The adhesion performance of the products prepared in the embodiments and comparative examples of the present invention (with an average coating thickness of 2 micrometers) was tested. The specific test method was as follows: the effective abrasion resistance number of the samples was tested using an abrasion resistance tester. The test conditions were: TABER CS-5 wool felt, stroke 5cm, speed 60r / min, and load 500g. The effective abrasion resistance number was defined as the critical value of the water droplet angle being 100°.

[0184] (4) Transmittance performance test

[0185] The transmittance performance of the products prepared in the embodiments and comparative examples of the present invention (with an average coating thickness of 2 micrometers) was tested. The specific test method was as follows: the transmittance of the transparent substrate was determined according to GB / T 5433-2008 "Method for Determination of Light Transmittance of Daily Use Glass".

[0186] The test results are shown in Table 1 below.

[0187] Table 1: Performance tests of coatings prepared in the examples and comparative examples

[0188]

[0189] Analysis of the performance test data from the above embodiments and comparative examples shows that the antibacterial component of acrylate can impart good antibacterial effect to the coating, while the hydrophobic component of acrylate can impart good antifouling effect. As the amount of antibacterial unit of acrylate increases, the antibacterial rate improves; as the amount of hydrophobic unit of acrylate increases, the antifouling performance improves. However, increasing the amount of both leads to varying degrees of decrease in the transmittance of the transparent substrate, i.e., reduced transparency. The antibacterial unit of acrylate has the greatest impact on the transparent substrate; excessive antibacterial units result in a significant decrease in substrate transparency. Furthermore, the coupling agent KH570 can improve the adhesion of the coating, but its amount affects the transparency of the substrate; the higher the amount of KH570, the lower the transparency. Therefore, a comprehensive consideration is needed while taking into account the substrate transparency. Among the application examples, Example 1 shows the best effect.

[0190] In this invention, the antibacterial effect decreases to some extent when the type of antibacterial component is changed. When the content of the antibacterial agent changes, the antibacterial effect is optimal when it is between 0.5 and 1.5 parts; below this range, the antibacterial effect decreases. In this invention, the hydrophobic effect is optimal when the content of the hydrophobic component is between 5 and 15 parts; below or above this content, the hydrophobic effect decreases significantly. Simultaneously, since the amount of antibacterial component significantly affects the transparency of the substrate, the introduction of the hydrophobic perfluoropolyether unit, due to its anti-bioadhesion properties, provides a certain degree of benefit to the antibacterial component. Therefore, without affecting the overall antibacterial effect, the amount of hydrophobic component can be increased while the amount of antibacterial component can be reduced, maximizing the transparency of the substrate. Therefore, the content of the antibacterial component is more preferably 0.5 to 1 part, and the content of the hydrophobic component is more preferably 10 to 15 parts.

[0191] The above description is merely a preferred embodiment of the present invention, and the present invention is not limited to the above embodiments. It is understood that other improvements and variations that are directly derived or conceived by those skilled in the art without departing from the spirit and concept of the present invention should be considered to be included within the protection scope of the present invention.

Claims

1. A long-lasting antibacterial and antifouling acrylic resin modified coating material, characterized in that, By mass, it consists of the following raw material components: 0.5 to 2 parts of an antibacterial unit containing acrylate; 5 to 20 parts of hydrophobic units containing acrylate; 0.5 to 2 parts coupling agent; 35 to 50 parts of multifunctional polyurethane acrylate; 30-40 parts reactive diluent; Initiator: 0.1 to 0.3 parts; 10 to 30 parts organic solvent; The coupling agent is silane coupling agent KH570; The general structural formula of the acrylate-containing antimicrobial unit is shown in formula (Ⅰ) below: （Ⅰ） The R is selected from any of the following groups: (1) (2) (3) (4) (5)； The acrylate-containing hydrophobic unit is obtained by reacting acryloyl chloride with perfluoropolyether alcohol, the CAS number of which is 90317-77-4.

2. The long-lasting antibacterial and antifouling acrylic resin modified coating material according to claim 1, characterized in that, The initiator includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone; the multifunctional polyurethane acrylate has a functionality of 4 to 6; the reactive diluent includes one or more of methyl acrylate, ethyl acrylate, and methyl methacrylate; and the organic solvent includes one or two of ethyl acetate and n-butyl acetate.

3. The long-lasting antibacterial and antifouling acrylic resin modified coating material according to claim 1, characterized in that, The initiator is 2-hydroxy-2-methyl-1-phenylpropanone.

4. The long-lasting antibacterial and antifouling acrylic resin modified coating material according to claim 1, characterized in that, The reactive diluent is methyl methacrylate.

5. The long-lasting antibacterial and antifouling acrylic resin modified coating material according to claim 1, characterized in that, The organic solvent is n-butyl acetate.

6. A method for preparing the long-lasting antibacterial and antifouling acrylic resin modified coating material according to any one of claims 1 to 5, characterized in that, The method is as follows: S1: Preparation of antibacterial units containing acrylate; S2: Preparation of hydrophobic units containing acrylates; S3: By weight, mix 0.5 to 2 parts of antibacterial unit containing acrylate, 5 to 20 parts of hydrophobic unit containing acrylate, 0.5 to 2 parts of coupling agent, 35 to 50 parts of multifunctional polyurethane acrylate, 30 to 40 parts of reactive diluent, 0.1 to 0.3 parts of initiator, and 10 to 30 parts of organic solvent, and stir at 25 to 50°C for 15 to 60 minutes to obtain a long-lasting antibacterial and antifouling acrylic resin modified coating material.

7. The method according to claim 6, characterized in that, The method for preparing the acrylate-containing antibacterial unit is as follows: phenolic antibacterial agent is mixed evenly with solvent and acid-binding agent, then acryloyl chloride is added dropwise in an ice bath, and the mixture is reacted at 25~50℃ for 2~4 hours. Excess solvent is removed by rotary evaporation, followed by extraction and purification, drying, filtration, and further solvent removal by rotary evaporation to obtain the acrylate-containing antibacterial unit.

8. The method according to claim 7, characterized in that, The phenolic antibacterial agents include one or more of 5-chloro-2-(2,4-dichlorophenoxy)phenol, p-chloro-m-xylenol, 3-methyl-4-isopropylphenol, 5-isopropyl-2-methylphenol, and 2,4-dichloro-3,5-dimethylphenol. The acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate; The solvent includes one or more of dichloromethane, tetrahydrofuran, and xylene.

9. The method according to claim 7, characterized in that, The phenolic antibacterial agent is 5-chloro-2-(2,4-dichlorophenoxy)phenol.

10. The method according to claim 7, characterized in that, The acid-binding agent is potassium carbonate.

11. The method according to claim 7, characterized in that, The solvent is dichloromethane.

12. The method according to claim 7, characterized in that, The mass-to-volume ratio of the phenolic antibacterial agent to the solvent is 10g:15mL to 10g:30mL. The mass ratio of the phenolic antibacterial agent to acryloyl chloride is 10:4 to 10:9; The mass ratio of the acid-binding agent to acryloyl chloride is 10:7 to 10:

14.

13. The method according to claim 6, characterized in that, The preparation method of the acrylate-containing hydrophobic unit is as follows: a perfluoropolyether alcohol is mixed evenly with a fluorinated solvent and an acid-binding agent, acryloyl chloride is added dropwise in an ice bath and reacted at 25~50℃. After the reaction is completed, the mixture is first extracted and then rotary evaporated to remove excess solvent. Then, it is extracted with methanol and SV70 and rotary evaporated to remove excess solvent to obtain the acrylate-containing hydrophobic unit. The fluorinated solvent includes one or more of nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, tridecafluorohexyl methyl ether, hydrofluoroether, and m-difluorotoluene; The acid-binding agent includes one or more of triethylamine, N-ethyldiisopropylamine, pyridine, potassium carbonate, and sodium carbonate; The mass-to-volume ratio of the perfluorinated polyether alcohol to the fluorinated solvent is 10g:15mL to 10g:30mL. The mass ratio of the perfluoropolyether alcohol to acryloyl chloride is 10:0.4 to 10:1; The mass ratio of perfluoropolyether alcohol to acid-binding agent is 10:0.7~10:

1.

14. The method according to claim 13, characterized in that, The acid-binding agent is potassium carbonate.

15. The application of a long-lasting antibacterial and antifouling acrylic resin modified coating material prepared by the method of any one of claims 6 to 14, or the long-lasting antibacterial and antifouling acrylic resin modified coating material of any one of claims 1 to 5, characterized in that, The long-lasting antibacterial and antifouling acrylic resin modified coating material is used to prepare a long-lasting antibacterial and antifouling acrylic resin modified coating.

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