Hydrophilic antibacterial mildew inhibitor, synthetic method thereof, mildew-proof antibacterial hydrophilic coating and application thereof

Abstract

The invention belongs to the technical field of coating materials, and particularly relates to a hydrophilic antibacterial mildew-proof agent, a synthesis method thereof, a mildew-proof antibacterial hydrophilic coating and application thereof. The preparation raw materials comprise thymol and glycidyl methacrylate. According to the hydrophilic antibacterial and mildew-proof agent provided by the invention, thymol with antibacterial performance is grafted with glycidyl methacrylate, and double bonds in the hydrophilic antibacterial and mildew-proof agent provide active sites for subsequent reaction with acrylic resin and a curing agent; a cross-linking reaction with acrylic resin and a curing agent in the coating can be carried out to form a cross-linked structure with an antibacterial effect; the cross-linked structure can also improve the stability and mechanical properties of the coating, and can still maintain the structural integrity in a complex environment, thereby continuously playing an antibacterial role and effectively inhibiting the growth of various moulds and bacteria.

Description

Technical Field

[0001] This invention belongs to the field of coating materials technology, specifically relating to a hydrophilic antibacterial and antifungal agent and its synthesis method, an antifungal and antibacterial hydrophilic coating and its application. Background Technology

[0002] Air conditioners are widely used in modern life, and aluminum foil, as a key material for air conditioner radiator fins, directly affects the air conditioner's heat dissipation efficiency and lifespan. As people's demands for quality of life increase, in addition to basic heat dissipation performance, the anti-mold, antibacterial, and hydrophilic properties of air conditioner aluminum foil are becoming increasingly important. In humid environments, mold and bacteria easily grow inside air conditioners. These microorganisms not only produce odors but can also spread with the air blown out by the air conditioner, affecting indoor air quality and harming human health.

[0003] To address this issue, most existing technologies achieve antifungal and antibacterial effects in coatings through physical mixing or grafting quaternary ammonium salts. For example, patent publication CN112724770A describes copolymerizing antibacterial quaternary ammonium salt monomers with acrylic monomers to generate a structural antibacterial acrylic resin. This resin is then mixed with antibacterial inorganic nanomaterials, a curing agent, a wetting agent, a co-solvent, and water to obtain an antibacterial, antifungal, and hydrophilic coating. However, physical mixing has two major drawbacks: first, the antibacterial agent has poor compatibility with the coating matrix, easily migrating and precipitating, resulting in a short antibacterial effective period, failing to meet the requirements of long-term air conditioning use; second, some small-molecule antibacterial agents are prone to decomposition and inactivation under high temperature and humidity environments, potentially posing environmental toxicity or biosafety risks. Furthermore, the quaternary ammonium salt copolymerization grafting method has a limited antibacterial spectrum, with weak inhibitory effects against spore-forming bacteria or some halophilic molds, and long-term use of quaternary ammonium salts carries the risk of developing drug resistance.

[0004] In patent publication CN103865276A, thymol and β-cyclodextrin molecules are selected and prepared using a saturated aqueous solution method, followed by incubation and shaking, and then spray drying to form an inclusion complex. In the preparation of an antibacterial edible packaging film, the inclusion complex is added to a film-forming solution using gelatin as a carrier, and the film is cast and dried under natural conditions to prepare an antibacterial edible packaging with controlled release function. While encapsulating thymol with cyclodextrin molecules can achieve a sustained-release effect, air conditioning requires processing to remove volatile oils, and during long-term use, it is subject to repeated rinsing by condensation. Therefore, physical encapsulation alone is insufficient to achieve a long-term stable anti-mold and antibacterial effect. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a hydrophilic antibacterial and antifungal agent and its synthesis method, as well as an antifungal and antibacterial hydrophilic coating and its application. This aims to solve at least one of the above-mentioned technical problems.

[0006] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a hydrophilic antibacterial and antifungal agent with the following structural formula: .

[0007] Secondly, the present invention provides a method for synthesizing the above-mentioned hydrophilic antibacterial and antifungal agent, comprising the following steps: The mixture of thymol and glycidyl methacrylate was reacted and then purified.

[0008] Thirdly, the present invention provides a mildew-proof and antibacterial hydrophilic coating, comprising the following raw materials in parts by weight: 30-55 parts acrylic copolymer resin, 8-12 parts propylene glycol n-propyl ether, 0.3-0.7 parts sodium primary alkyl sulfonate, 0.3-0.7 parts Tween 85, 0.8-1.2 parts curing agent, 0.8-1.2 parts antibacterial and antifungal agent, 0.8-1.2 parts nano silver solution, 30-55 parts water; The antibacterial and antifungal agents include the hydrophilic antibacterial and antifungal agents described above.

[0009] Fourthly, the present invention provides an application of the above-mentioned anti-mildew and antibacterial hydrophilic coating in the field of coating materials.

[0010] The hydrophilic antibacterial and antifungal agent provided by this invention has at least the following beneficial technical effects compared with the prior art: The hydrophilic antibacterial and antifungal agent provided by this invention grafts glycidyl methacrylate with thymol, which has antibacterial properties. The double bonds in the hydrophilic antibacterial and antifungal agent provide active sites for subsequent reactions with acrylic resin and curing agent, enabling it to cross-link with acrylic resin and curing agent in coatings to form a cross-linked structure with antibacterial effect. This cross-linked structure can also improve the stability and mechanical properties of the coating, and maintain its structural integrity in complex environments, thereby continuously exerting antibacterial effects and effectively inhibiting the growth of various molds and bacteria.

[0011] The anti-mildew and antibacterial hydrophilic coating provided by this invention has at least the following beneficial technical effects compared with the prior art: The antifungal and antibacterial hydrophilic coating provided by this invention utilizes the hydrophilic antibacterial and antifungal agent provided by this invention, which undergoes a cross-linking reaction with acrylic resin and a curing agent. The cross-linked structure formed after the reaction with the acrylic resin and curing agent gives the coating high stability and mechanical properties, which is crucial for the durability of antibacterial materials in practical applications. In real-world environments, antibacterial materials may be affected by various physical and chemical factors, such as humidity, temperature, and the usage environment. A stable cross-linked structure ensures that the antibacterial material maintains its structural integrity under these complex environments, thus continuously exerting its antibacterial effect. It can effectively inhibit the growth of various molds and bacteria, such as Staphylococcus aureus and Escherichia coli, reducing the possibility of odor generation inside air conditioners and ensuring indoor air quality. The acrylic copolymer resin has good hydrophilic properties, allowing condensate to spread and flow quickly on the surface of the air conditioner's aluminum foil, preventing water accumulation and further preventing microbial growth, while also improving the heat exchange efficiency of the air conditioner. Nano-silver, with its highly efficient antibacterial properties, compensates for the potential limitations of thymol's antibacterial spectrum and works synergistically with the antibacterial and antifungal agent and the acrylic copolymer resin. In the coating, nano-silver is uniformly dispersed in the coating layer and continuously releases silver ions, which effectively kills mold and bacteria in the surrounding environment. It destroys the living environment and physiological functions of microorganisms from multiple aspects, achieving a highly efficient and long-lasting anti-mold and antibacterial effect. Detailed Implementation

[0012] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0013] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0014] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0015] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0016] Hydrophilic antibacterial and antifungal agent The first aspect of this invention provides a hydrophilic antibacterial and antifungal agent with the following structural formula: .

[0017] The hydrophilic antibacterial and antifungal agent provided in this invention grafts glycidyl methacrylate with thymol, which has antibacterial properties. The double bonds in the hydrophilic antibacterial and antifungal agent provide active sites for subsequent reactions with acrylic resin and curing agent, enabling it to cross-link with acrylic resin and curing agent in the coating to form a cross-linked structure with antibacterial effect. This cross-linked structure can also improve the stability and mechanical properties of the coating, and maintain its structural integrity in complex environments, thereby continuously exerting antibacterial effects and effectively inhibiting the growth of various molds and bacteria.

[0018] In some embodiments, a hydrophilic antibacterial and antifungal agent is provided, the raw materials for which are prepared include: Thymol and glycidyl methacrylate.

[0019] In some embodiments, the molar ratio of thymol to glycidyl methacrylate is 1:(1.5~2).

[0020] In some preferred embodiments, the molar ratio of thymol to glycidyl methacrylate is 1:1.5.

[0021] In some embodiments, the CAS number of thymol is 89-83-8.

[0022] In some embodiments, the CAS number of glycidyl methacrylate is 106-91-2.

[0023] Synthesis methods of hydrophilic antibacterial and antifungal agents A second aspect of this invention provides a method for synthesizing a hydrophilic antibacterial and antifungal agent, comprising the following steps: S10. Thymol and glycidyl methacrylate were mixed and reacted and then purified.

[0024] In some embodiments, in step S10 above, the mixing reaction includes the following steps: S101. A mixture of thymol, glycidyl methacrylate, and catalyst is stirred and reacted under an inert atmosphere.

[0025] In some embodiments, in step S101 above, the inert atmosphere includes one of nitrogen, argon, and helium.

[0026] In some embodiments, in step S101 described above, the catalyst comprises triphenylphosphine.

[0027] In some embodiments, in step S101 above, the mass of the catalyst is 0.5% to 0.6% of the mass of thymol.

[0028] In some preferred embodiments, in step S101 above, the mass of the catalyst is 0.5% of the mass of thymol.

[0029] In some embodiments, in step S101 above, the heating rate of the stirring reaction is 0.5℃ / min to 3℃ / min.

[0030] In some embodiments, in step S101 above, the temperature of the stirring reaction is 80°C to 90°C.

[0031] In some embodiments, in step S101 above, the stirring reaction time is 3h to 5h.

[0032] In some embodiments, in step S10 above, purification includes the following steps: S102. The product after the mixed reaction is mixed with ethyl acetate to obtain a diluted solution; The diluted material was washed and then dried.

[0033] In some embodiments, in step S102 above, the mass ratio of ethyl acetate to the total mass of thymol and glycidyl methacrylate is (1~1.2):1.

[0034] In some embodiments, in step S102 above, the washing process includes the following steps: S1021. Wash the diluted substance sequentially with saturated sodium bicarbonate solution and water to obtain the organic phase.

[0035] In some embodiments, in step S1021 above, the mass ratio of the saturated sodium bicarbonate solution to the total mass of thymol and glycidyl methacrylate is (1~1.2):1.

[0036] In some embodiments, in step S1021 above, the mass ratio of water to the total mass of thymol and glycidyl methacrylate is (1~1.2):1.

[0037] In some embodiments, the drying process in step S102 above includes the following steps: S1022. After the organic phase obtained from the washing treatment is mixed with the desiccant, the supernatant is taken for vacuum distillation.

[0038] In the above drying process, the organic phase and the desiccant are mixed to remove the residual moisture in the organic phase, and the organic solvent (ethyl acetate, etc.) is removed by vacuum distillation to obtain a dried hydrophilic antibacterial and antifungal agent.

[0039] In some embodiments, in step S1022 above, the desiccant includes at least one of anhydrous sodium sulfate and anhydrous magnesium sulfate.

[0040] In some embodiments, in step S1022 above, the amount of desiccant used is 0.5% to 3% of the mass of the organic phase.

[0041]

Anti-mildew, antibacterial, and hydrophilic coating

[0042] The antifungal and antibacterial hydrophilic coating provided in this invention uses a hydrophilic antibacterial and antifungal agent, which undergoes a cross-linking reaction with acrylic resin and a curing agent. The cross-linked structure formed after the reaction gives the coating high stability and mechanical properties, which is crucial for the durability of antibacterial materials in practical applications. In real-world environments, antibacterial materials may be affected by various physical and chemical factors, such as humidity, temperature, and the usage environment. A stable cross-linked structure ensures that the antibacterial material maintains its structural integrity under these complex environments, thus continuously exerting its antibacterial effect. It can effectively inhibit the growth of various molds and bacteria, such as Staphylococcus aureus and Escherichia coli, reducing the possibility of odor generation inside air conditioners and ensuring indoor air quality. The acrylic copolymer resin has good hydrophilic properties, allowing condensate to spread and flow quickly on the surface of the air conditioner's aluminum foil, preventing water accumulation and further preventing microbial growth, while also improving the heat exchange efficiency of the air conditioner. Nano-silver, with its highly efficient antibacterial properties, compensates for the potential limitations of thymol's antibacterial spectrum and works synergistically with the antibacterial and antifungal agent and the acrylic copolymer resin. In the coating, nano-silver is uniformly dispersed in the coating layer and continuously releases silver ions, which effectively kills mold and bacteria in the surrounding environment. It destroys the living environment and physiological functions of microorganisms from multiple aspects, achieving a highly efficient and long-lasting anti-mold and antibacterial effect.

[0043] In some preferred embodiments, the antifungal and antibacterial hydrophilic coating comprises the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part antibacterial and antifungal agent, 1 part nano silver solution, 40 parts water.

[0044] In some embodiments, the raw materials for preparing the acrylic copolymer resin include: Monomer mixtures, initiators, and terminating agents; The monomer mixture includes hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, styrene, and acrylic acid.

[0045] In some embodiments, the molar ratio of hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, styrene, and acrylic acid is (2~6):(1~2.5):(3~10):(2~5.5):1.

[0046] In some preferred embodiments, the molar ratio of hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, styrene, and acrylic acid is 2:1:3:2:1.

[0047] In some embodiments, the CAS number of hydroxypropyl acrylate is 999-61-1.

[0048] In some embodiments, the CAS number of potassium propyl 3-sulfonate methacrylate is 31098-21-2.

[0049] In some embodiments, the CAS number for butyl acrylate is 141-32-2.

[0050] In some embodiments, the CAS number for styrene is 100-42-5.

[0051] In some embodiments, acrylic acid has the CAS number 79-10-7.

[0052] In some embodiments, the initiator includes azobisisobutyronitrile (AIBN).

[0053] In some embodiments, the CAS number of azobisisobutyronitrile is 75804-30-7.

[0054] In some embodiments, the mass of the initiator is 0.5% to 0.6% of the mass of the monomer mixture, preferably 0.5%.

[0055] In some embodiments, the terminating agent includes hydroquinone.

[0056] In some embodiments, hydroquinone has the CAS number 123-31-9.

[0057] In some embodiments, the mass of the terminating agent is 0.02% to 0.03% of the mass of the monomer mixture, preferably 0.02%.

[0058] In some embodiments, Tween 85 has the CAS number 9005-70-3.

[0059] In some embodiments, the curing agent includes Cymel 1156, a curing agent manufactured by Allnex Corporation of the United States.

[0060] In some embodiments, the nano-silver solution includes the nano-silver solution JDTKS-001 produced by Jinda Technology Co., Ltd.

[0061] Preparation method of anti-mildew and antibacterial hydrophilic coating A fourth aspect of this invention provides a method for preparing an anti-mildew and antibacterial hydrophilic coating, comprising the following steps: s10. Mix acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent, nano silver solution and water according to the preset ratio.

[0062] In some embodiments, the preparation of the acrylic copolymer resin in step s10 above includes the following steps: s101. The first polymerizing monomer and toluene are mixed to obtain a mixture of the first polymerizing monomer; The first monomers include hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, and styrene.

[0063] s102. The initiator and toluene are mixed to obtain an initiator solution.

[0064] s103. Acrylic monomer and toluene are mixed to obtain an acrylic monomer mixture.

[0065] s104. Take 20% to 50% of the total mass of the initiator solution and the first polymerizable monomer mixture, perform a first mixing treatment, and then perform a first polymerization reaction treatment to obtain the first polymer solution.

[0066] s105. The remaining initiator solution, acrylic monomer mixture and first polymerization solution are subjected to a second mixing treatment and then subjected to a second polymerization reaction treatment to obtain a second polymerization solution.

[0067] s106. The second polymerization liquid and the terminating agent are mixed to stop the reaction, resulting in a reaction solution.

[0068] s107. The reaction solution was purified to obtain an acrylic copolymer resin.

[0069] In some embodiments, in step s101 above, the mass fraction of the first polymeric monomer in the first polymeric monomer mixture is 20% to 60%.

[0070] In some embodiments, in step s102 above, the mass concentration of the initiator in the initiator solution is 2% to 5%.

[0071] In some embodiments, in step s103 above, the mass fraction of acrylic monomer in the acrylic monomer mixture is 15-50%.

[0072] In some embodiments, in step s104 above, the first mixing process includes the following steps: s1041. Under stirring, 20% to 50% of the total mass of the initiator solution is added dropwise to the first monomer mixture over a period of 0.5 to 2 hours to obtain the first mixture.

[0073] It should be noted that in step s1041, stirring is a conventional mixing method in the art and is not particularly limited in the embodiments of the present invention.

[0074] In some embodiments, in step s104 above, the first polymerization reaction treatment includes the following steps: s1042. The first mixture was reacted at 60℃~90℃ for 0.5h~3h under stirring at 110rpm~350rpm.

[0075] It should be noted that in step s1042, stirring is a conventional mixing method in the art and is not particularly limited in the embodiments of the present invention.

[0076] In some embodiments, in step s105 above, the second mixing process includes the following steps: s1051. Under stirring, the remaining initiator solution and acrylic monomer mixture are added dropwise to the first polymerization solution over a period of 1 to 3 hours to obtain the second mixture.

[0077] It should be noted that in step s1051, stirring is a conventional mixing method in the art and is not particularly limited in the embodiments of the present invention.

[0078] In some embodiments, in step s105 above, the second polymerization reaction treatment includes the following steps: s1052. Under stirring, the second mixture reacts at 60℃~90℃ for 2h~4h.

[0079] In some embodiments, in step s106 above, the reaction termination process includes the following steps: s1061. The second polymerization solution and the stop agent are mixed at 55℃~65℃ and reacted for 0.5h~2h.

[0080] In some embodiments, in step s107 above, purification includes the following steps: s1071. After mixing the reaction solution and the precipitant, the precipitate is obtained and washed until the filtrate after the last wash is clear and transparent, and has the same appearance as the precipitant, without oily turbidity or milky white suspended matter, and dried to constant weight.

[0081] In some embodiments, in step s1071 above, the precipitant includes at least one of methanol and ethanol.

[0082] In some embodiments, in step s1071 above, the amount of precipitant used is 3 to 5 times the amount of reaction solution used.

[0083] In some embodiments, in step s1071 above, the precipitate is washed with a precipitant.

[0084] In some embodiments, in step s1071 above, the drying temperature is 65°C to 90°C.

[0085] In some embodiments, in step s1071 above, the drying is vacuum drying.

[0086] The following description, in conjunction with specific embodiments, provides further details.

[0087] For ease of explanation, in the following embodiments and comparative examples: (1) The selected acrylic copolymer resin is prepared by the following method: 1) The first monomer and toluene are mixed to obtain a first monomer mixture with a mass fraction of 40%; The first monomer is hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, styrene, and acrylic acid in a molar ratio of 2:1:3:2:1.

[0088] 2) Azobisisobutyronitrile and toluene are mixed to obtain an initiator solution with a mass fraction of 30%.

[0089] 3) The acrylic monomer and toluene are mixed to obtain an acrylic monomer mixture with a mass fraction of 50%.

[0090] 4) First mixing treatment: Under stirring, 40% of the total mass of the initiator solution is added dropwise to the first monomer mixture over a period of 1 hour to obtain the first mixture.

[0091] 5) First polymerization reaction treatment: The first mixture was reacted at 95°C for 2 hours under stirring at 200 rpm to obtain the first polymerization solution.

[0092] 6) Second mixing treatment: Under stirring, the remaining initiator solution and acrylic monomer mixture are added dropwise to the first polymerization solution, with a total addition time of 3 hours, to obtain the second mixture.

[0093] 7) Second polymerization reaction treatment: Under stirring, the second mixture is reacted at 95°C for 3 hours to obtain the second polymerization solution.

[0094] 8) The second polymerization liquid and the stop agent are mixed at 55℃~65℃ and reacted for 1 hour to obtain the reaction solution.

[0095] 9) Mix the reaction solution with ethanol at a volume of 3 times the mass of the reaction solution, filter, and wash several times with a precipitant until the filtrate after the last wash is clear and transparent, and has the same appearance as the precipitant, without oily turbidity or milky white suspended matter. Then, vacuum dry at 80°C to constant weight to obtain acrylic copolymer resin.

[0096] (2) The CAS number of thymol is 89-83-8.

[0097] (3) The CAS number of glycidyl methacrylate is 106-91-2.

[0098] (4) The CAS number of hydroxypropyl acrylate is 999-61-1.

[0099] (5) The CAS number of potassium methyl methacrylate 3-sulfonate is 31098-21-2.

[0100] (6) The CAS number of butyl acrylate is 141-32-2.

[0101] (7) The CAS number for styrene is 100-42-5.

[0102] (8) The CAS number of acrylic acid is 79-10-7.

[0103] (9) The CAS number of azobisisobutyronitrile is 75804-30-7.

[0104] (10) Hydroquinone’s CAS number is 123-31-9.

[0105] (11) The CAS number of Tween 85 is 9005-70-3.

[0106] (12) The curing agent is Cymel 1156 manufactured by Allnex, Inc.

[0107] (13) The nano silver solution is JDTKS-001 produced by Jinda Technology Co., Ltd.

[0108] Example 1 Example 1 provides a hydrophilic antibacterial and antifungal agent with the following structural formula: .

[0109] The hydrophilic antibacterial and antifungal agent is prepared from thymol and glycidyl methacrylate in a molar ratio of 1:1.5.

[0110] This embodiment also provides a method for synthesizing the above-mentioned hydrophilic antibacterial and antifungal agent, the steps of which are as follows: E10. Mixed reaction: A mixture of thymol, glycidyl methacrylate and triphenylphosphine catalyst is stirred and reacted under a nitrogen atmosphere; Of which, the mass of triphenylphosphine is 0.5% of the mass of thymol; The stirring reaction was carried out at a heating rate of 1℃ / min, a temperature of 90℃, and a time of 4.5h.

[0111] E20. Purification E201. Dilution: The product after the mixed reaction is mixed with ethyl acetate to obtain a diluted product; wherein the mass ratio of ethyl acetate to the total mass of thymol and glycidyl methacrylate is 1:1.

[0112] E202. Washing treatment: The diluted substance is washed sequentially with saturated sodium bicarbonate solution and water to obtain the organic phase; wherein the mass ratio of the saturated sodium bicarbonate solution to the total mass of thymol and glycidyl methacrylate is 1:1; the mass ratio of the water to the total mass of thymol and glycidyl methacrylate is 1:1.

[0113] E203. Drying treatment: After mixing the organic phase and anhydrous sodium sulfate, the supernatant was taken and subjected to vacuum distillation to obtain the hydrophilic antibacterial and antifungal agent of this embodiment; The amount of anhydrous sodium sulfate used is 10% of the mass of the organic phase.

[0114] Example 2 Example 2 provides a mildew-proof and antibacterial hydrophilic coating, composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part antibacterial and antifungal agent, 1 part nano silver solution, 40 parts water; The antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1.

[0115] A10. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent, nano silver solution and water according to the preset weight proportions.

[0116] Example 3 Example 3 provides a mildew-proof and antibacterial hydrophilic coating, composed of the following raw materials in parts by weight: 30 parts acrylic copolymer resin, 8 parts propylene glycol n-propyl ether, 0.3 parts sodium primary alkyl sulfonate, 0.3 parts Tween 85, 0.8 parts curing agent, 0.8 parts antibacterial and antifungal agent, 0.8 parts nano silver solution, 30 parts water; The antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1.

[0117] This embodiment also provides a method for preparing the above-mentioned anti-mildew and antibacterial hydrophilic coating, the steps of which are as follows: A11. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent, nano silver solution and water according to the preset weight proportions.

[0118] Example 4 Example 4 provides a mildew-proof and antibacterial hydrophilic coating, composed of the following raw materials in parts by weight: 55 parts acrylic copolymer resin, 12 parts propylene glycol n-propyl ether, 0.7 parts sodium primary alkyl sulfonate, 0.7 parts Tween 85, 1.2 parts curing agent, 1.2 parts antibacterial and antifungal agent, 1.2 parts nano silver solution, 55 parts water; The antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1.

[0119] This embodiment also provides a method for preparing the above-mentioned anti-mildew and antibacterial hydrophilic coating, the steps of which are as follows: A12. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent, nano silver solution and water according to the preset weight proportions.

[0120] Comparative Example 1 Comparative Example 1 provides a coating composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part thymol, 1 part nano silver solution, 40 parts water.

[0121] This comparative example also provides a method for preparing the above-mentioned coating, the steps of which are as follows: D10. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, thymol, nano silver solution and water according to the preset weight proportions.

[0122] Comparative Example 2 Comparative Example 2 provides a coating composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part antibacterial and antifungal agent, 40 parts water; The antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1.

[0123] This comparative example also provides a method for preparing the above-mentioned coating, the steps of which are as follows: D11. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent and water according to the preset weight proportions.

[0124] Comparative Example 3 Comparative Example 3 provides a coating composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part antibacterial and antifungal agent, 1 part nano titanium dioxide, 40 parts water; The antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1; the particle size D50 of nano titanium dioxide is 30 nm.

[0125] This comparative example also provides a method for preparing the above-mentioned coating, the steps of which are as follows: D12. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, antibacterial and antifungal agent, nano titanium dioxide and water according to the preset weight proportions.

[0126] Comparative Example 4 Example 4 provides a coating composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part Kathon, 1 part nano silver solution, 40 parts water; Among them, the antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1; Kathon is isothiazolinone (Kathon) produced by Shanghai Huao Industrial Co., Ltd., model number HUAOSH® KS25.

[0127] This comparative example also provides a method for preparing the above-mentioned coating, the steps of which are as follows: D13. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, Kathon, nano silver solution and water according to the preset weight proportions.

[0128] Comparative Example 5 Example 5 provides a coating composed of the following raw materials in parts by weight: 40 parts acrylic copolymer resin, 10 parts propylene glycol n-propyl ether, 0.5 parts sodium primary alkyl sulfonate, 0.5 parts Tween 85, 1 part curing agent, 1 part nano silver solution, 40 parts water; Among them, the antibacterial and antifungal agent is the hydrophilic antibacterial and antifungal agent provided in Example 1; Kathon is isothiazolinone (Kathon) produced by Shanghai Huao Industrial Co., Ltd., model number HUAOSH® KS25.

[0129] This comparative example also provides a method for preparing the above-mentioned coating, the steps of which are as follows: D14. Mix the acrylic copolymer resin, propylene glycol n-propyl ether, sodium primary alkyl sulfonate, Tween 85, curing agent, nano silver solution and water according to the preset weight proportions.

[0130] To verify the advancements of the hydrophilic antibacterial and antifungal agent and its synthesis method, as well as the antifungal and antibacterial hydrophilic coating and its preparation method provided in the embodiments of the present invention, the hydrophilicity, antifungal properties, and antibacterial properties of the antifungal and antibacterial hydrophilic coatings provided in the embodiments and comparative examples of the present invention were tested after being made into coatings. The results are shown in Table 1 below.

[0131] in: The coating preparation steps are as follows: The coating material is roller-coated onto the surface of the air conditioner aluminum foil, and after curing, a coating with a thickness of 1μm±0.1μm is obtained.

[0132] Table 1

[0133] Note: Initial hydrophilic angle refers to the angle formed when a droplet stands upright on the aluminum foil surface before the aluminum foil undergoes finning. A smaller hydrophilic angle indicates better hydrophilicity; conversely, a larger hydrophilic angle indicates poorer hydrophilicity. Processed hydrophilic angle refers to the angle formed between the droplet and the aluminum foil surface after the aluminum foil has been finned.

[0134] From Table 1 above, at least the following conclusions can be drawn: (1) As can be seen from the data in the table, Comparative Example 1 did not use the thymol-grafted glycidyl methacrylate antibacterial and antifungal agent of the present invention, but only directly added thymol. Its initial hydrophilic angle was 12°, the process hydrophilic angle was 20°, and after 100h of water flow test, the hydrophilic angle suddenly increased to 31°, the antifungal performance dropped from level 0 to level 1, and the antibacterial performance dropped from 99% to 92%. In contrast, in the examples, the initial antifungal and antibacterial performance was not much different from that after the test. It can be seen that the hydrophilic antibacterial and antifungal agent provided by the embodiments of the present invention grafts thymol with glycidyl methacrylate, which can undergo a cross-linking reaction with acrylic resin and curing agent to form a stable cross-linked structure. This structure not only greatly improves the durability of the coating's hydrophilicity, but also ensures the structural integrity of the antibacterial and antifungal components.

[0135] (2) Data from Example 2 and Comparative Example 2 show that Comparative Example 2, without the addition of nano-silver solution, exhibited a level 1 antifungal performance and a 98% antibacterial performance in both the initial stage and after 100 hours of water flow testing, which is lower than the level 0 antifungal performance and 99% antibacterial performance of Example 2. This indicates that nano-silver can effectively compensate for the limitations of the antibacterial spectrum of thymol. Its continuously released silver ions can synergistically work with thymol-based antibacterial and antifungal agents, disrupting the microbial living environment and physiological functions from multiple perspectives. The synergistic effect of the antibacterial spectrum of nano-silver and thymol can significantly enhance the antibacterial and antifungal efficacy of the coating.

[0136] (3) As can be seen from the data of Example 2 and Comparative Example 3, when nano-titanium dioxide was used instead of nano-silver solution in Comparative Example 3, the anti-mold performance was Grade 1 in both the initial stage of the coating and after 100 hours of water flow test, and the antibacterial performance decreased from 98% to 97%, which is significantly different from the Grade 0 anti-mold and 99% long-term antibacterial performance of Example 2. Therefore, compared with nano-titanium dioxide, the nano-silver solution has a greater advantage in antibacterial and anti-mold efficiency and durability in the hydrophilic antibacterial and anti-mold agent of the present invention, and is the optimal inorganic antibacterial component suitable for the hydrophilic antibacterial and anti-mold agent of the present invention.

[0137] (4) As can be seen from the data of Example 2 and Comparative Example 4, when Kathon was used instead of the antibacterial and antifungal agent of the present invention in Comparative Example 4, the initial antifungal performance of the coating was Grade 1 and the antibacterial performance was 95%. After 100 hours of water flow test, the antibacterial performance further decreased to 91%. It can be seen that compared with the traditional Kathon antibacterial agent, the hydrophilic antibacterial and antifungal agent of the present invention has a cross-linked structure with acrylic resin and curing agent, which makes it more stable in the coating and will not be lost or fail due to environmental factors. The antibacterial and antifungal effect and durability are significantly improved, and the synergistic effect with nano silver is better.

[0138] (5) In the preparation of the acrylic copolymer resin of the present invention, potassium propyl methacrylate is selected as the hydrophilic monomer. Its sulfonate group can give the coating excellent hydrophilic properties, so that the condensate can spread and flow down quickly on the surface of the air conditioner aluminum foil, avoiding water accumulation and microbial growth, and laying a solid environmental foundation for the synergistic antibacterial effect of antibacterial and antifungal agents and nano silver. When the monomer is polymerized with hydroxypropyl acrylate, butyl acrylate, styrene and acrylic acid in a molar ratio of 1:2:3:2:1 (that is, the molar ratio of hydroxypropyl acrylate, potassium propyl methacrylate, butyl acrylate, styrene and acrylic acid is 2:1:3:2:1), the copolymer resin obtained not only has the best hydrophilicity and film-forming properties, but also provides the best compatibility for antibacterial and antifungal agents and nano silver, ensuring that the two are uniformly dispersed and stably combined in the coating, giving full play to the synergistic effect of silver ions and thymol-based antibacterial and antifungal agents, destroying the conditions for the survival and reproduction of microorganisms from multiple aspects, and improving the heat exchange efficiency of air conditioners, laying a core foundation for the comprehensive performance of the coating.

[0139] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A hydrophilic antibacterial and antifungal agent, characterized in that, The structure is as follows: 。 2. The hydrophilic antibacterial and antifungal agent according to claim 1, characterized in that, The raw materials for preparation include: Thymol and glycidyl methacrylate.

3. The hydrophilic antibacterial and antifungal agent according to claim 2, characterized in that, The molar ratio of thymol to glycidyl methacrylate is 1:1.5~2.

4. A method for synthesizing the hydrophilic antibacterial and antifungal agent as described in any one of claims 1 to 3, characterized in that, Includes the following steps: The mixture of thymol and glycidyl methacrylate was reacted and then purified.

5. The method for synthesizing the hydrophilic antibacterial and antifungal agent according to claim 4, characterized in that, The mixing reaction includes the following steps: A mixture of thymol, glycidyl methacrylate, and catalyst was stirred and reacted under an inert atmosphere.

6. The method for synthesizing the hydrophilic antibacterial and antifungal agent according to claim 5, characterized in that, It satisfies at least one of the following characteristics (1) to (6): (1) The inert atmosphere includes one of nitrogen, argon, and helium; (2) The catalyst includes triphenylphosphine; (3) The mass of the catalyst is 0.5% to 0.6% of the mass of thymol; (4) The heating rate of the stirring reaction is 0.5℃ / min to 3℃ / min; (5) The temperature of the stirring reaction is 80℃~90℃; (6) The stirring reaction time is 3h~5h.

7. A mildew-proof and antibacterial hydrophilic coating, characterized in that, The raw materials include the following parts by weight: 30-55 parts acrylic copolymer resin, 8-12 parts propylene glycol n-propyl ether, 0.3-0.7 parts sodium primary alkyl sulfonate, 0.3-0.7 parts Tween 85, 0.8-1.2 parts curing agent, 0.8-1.2 parts antibacterial and antifungal agent, 0.8-1.2 parts nano silver solution, 30-55 parts water; The antibacterial and antifungal agent includes the hydrophilic antibacterial and antifungal agent according to any one of claims 1 to 3.

8. The anti-mildew and antibacterial hydrophilic coating according to claim 7, characterized in that, The raw materials for preparing the acrylic copolymer resin include: Monomer mixtures, initiators, and terminating agents; The monomer mixture includes hydroxypropyl acrylate, potassium propyl 3-sulfonate methacrylate, butyl acrylate, styrene, and acrylic acid.

9. The anti-mildew and antibacterial hydrophilic coating according to claim 8, characterized in that, It satisfies at least one of the following characteristics (1) to (5): (1) The molar ratio of hydroxypropyl acrylate, potassium propyl methacrylate 3-sulfonate, butyl acrylate, styrene, and acrylic acid is 2~6:1~2.5:3~10:2~5.5:1; (2) The initiator includes azobisisobutyronitrile; (3) The mass of the initiator is 0.5% to 0.6% of the mass of the monomer mixture; (4) The terminating agent includes hydroquinone; (5) The mass of the terminating agent is 0.02% to 0.03% of the mass of the monomer mixture.

10. The application of the anti-mildew and antibacterial hydrophilic coating as described in any one of claims 7 to 9 in the field of coating materials.

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