Broad-spectrum long-acting antibacterial mildew-proof coating as well as preparation method and application thereof

Abstract

The invention provides a broad-spectrum long-acting antibacterial mildew-proof coating as well as a preparation method and application thereof, and belongs to the technical field of antibacterial materials. According to the invention, the broad-spectrum long-acting antibacterial mildew-proof coating is simultaneously generated on the surface of the substrate through the borneol-based siloxane and the long-chain quaternary ammonium salt siloxane. Through'passive defense '(adhesion resistance) of the borneol structural unit and'active attack' (contact sterilization) of the long-chain quaternary ammonium salt, the limitation of a single antibacterial mechanism is solved, and particularly, the mildew-proof effect and the capacity of removing microorganisms are improved. The two active compounds form covalent bonds with a substrate through hydrolytic condensation of siloxane, and the coating is firm in combination, resistant to cleaning and abrasion and long in service life. By accurately regulating and controlling the ratio of the borneol-based siloxane to the quaternary ammonium salt siloxane, the antibacterial and mildew-proof performance of the coating on specific strains (such as bacteria and fungi) can be optimized, and the requirements of different application scenes are met.

Description

Technical Field

[0001] This invention relates to the field of antibacterial materials technology, and in particular to a broad-spectrum, long-lasting antibacterial and antifungal coating, its preparation method, and its application. Background Technology

[0002] Materials with hydroxyl functional groups on their surface are widely found in medical, packaging, home furnishing, and industrial fields, such as cellulose substrates (cotton fabrics, paper, etc.), polysaccharide materials, polymer films, wood, and metal oxides. Microorganisms such as bacteria, viruses, and fungi can easily adhere to and proliferate on these substrates. For example, microorganisms adhering to textile materials can potentially cause cross-infection of diseases. Microorganisms adhering to and proliferating on wood and polymer films will lead to a decline in material performance and reduced durability. To address these issues, researchers have investigated various methods for preparing antibacterial coatings.

[0003] Patent CN 113881086B utilizes a copolymer of bornyl acrylate and polyethylene glycol diacrylate to construct a polymeric coating with antimicrobial adhesion properties. However, this polymeric coating cannot kill bacteria; synergistic action between bornyl acrylate and polyethylene glycol diacrylate is required to effectively prevent microbial adhesion. Furthermore, the coating preparation process is complex: the first step involves fixing an initiator onto the building material surface, and the second step involves grafting monomers through surface free radical-initiated polymerization. Patent application CN 120966079 A, ​​through a surface grafting method, introduces a quaternary ammonium salt polymer with antibacterial properties onto the surface of a cellulose fiber membrane. Hexamethylene diisocyanate acts as a crosslinking agent to bond the hydroxyl groups of the small-molecule antibacterial agent to the hydroxyl groups on the cellulose surface, grafting a haloamine quaternary ammonium salt antibacterial agent onto the cellulose surface. The haloamine and quaternary ammonium salt exert a dual antibacterial effect. The preparation process starts with isonicotinic acid, which undergoes quaternization and ring-opening addition to obtain the quaternary ammonium salt intermediate of haloamine carboxylic acid pyridine. Then, cellulose grafting and halogenation are carried out. The preparation route is lengthy and the process is complex, and additional crosslinking agents are also required.

[0004] Although the aforementioned technical solutions have achieved some research results in the field of antibacterial coatings, they generally suffer from problems such as limited antibacterial function, complex preparation processes, high production costs, and low production efficiency. Therefore, how to prepare coatings with both bactericidal and anti-adhesion effects on material surfaces through simple chemical reactions, and which are universally applicable to various substrate materials containing hydroxyl groups, has become an urgent technical challenge to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide a broad-spectrum, long-lasting antibacterial and antifungal coating, its preparation method, and its application, so as to solve the problem that existing materials cannot simultaneously achieve efficient contact sterilization and long-lasting anti-adhesion functions.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a broad-spectrum, long-lasting antibacterial and antifungal coating, wherein the broad-spectrum, long-lasting antibacterial and antifungal coating is formed by compounding borneol-based siloxane and long-chain quaternary ammonium salt siloxane on the surface of a substrate, and the borneol-based siloxane has the structure shown in (1): (1)

[0008] R1 is selected from methyl or ethyl; The long-chain quaternary ammonium siloxane has the structure shown in (2): (2)

[0010] Wherein, R2 is selected from methyl or ethyl, and n is selected from an integer between 7 and 17.

[0011] Preferably, the surface of the substrate has hydroxyl groups.

[0012] This invention also provides a method for preparing the above-mentioned broad-spectrum long-lasting antibacterial and antifungal coating, comprising the following steps: (1) Mix borneol-based siloxane, long-chain quaternary ammonium salt siloxane and solvent to obtain a mixture; (2) Place the substrate in the mixture and carry out hydrolysis and curing reactions to obtain a broad-spectrum long-lasting antibacterial and antifungal coating.

[0013] Preferably, in step (1), the solvent is a mixed solvent of water and an alcohol compound, wherein the alcohol compound is methanol and / or isopropanol.

[0014] Preferably, in step (1), the mass ratio of borneol-based siloxane to long-chain quaternary ammonium siloxane is 0.1~1:0.1~1; and the concentration of borneol-based siloxane in the mixed solution is 2~25 mg / mL.

[0015] Preferably, the mass ratio of the borneol-based siloxane to the area of ​​the substrate is 0.1~1 g: 2500 mm². 2 .

[0016] Preferably, in step (2), the temperature of the hydrolysis reaction is 15~90℃ and the time of the hydrolysis reaction is 1~48h.

[0017] Preferably, in step (2), the curing reaction temperature is 50~200℃ and the curing reaction time is 0.5~1.5 h.

[0018] Preferably, in step (2), the curing reaction includes pre-curing and high-temperature curing; the pre-curing temperature is 70~90℃ and the pre-curing time is 1~10 min; the high-temperature curing temperature is 100~200℃ and the high-temperature curing time is 1~10 min.

[0019] The present invention also provides an application of the above-described broad-spectrum long-lasting antibacterial and antifungal coating in medical devices, food packaging, household or daily necessities.

[0020] The beneficial effects of this invention are: This invention effectively overcomes the limitations of a single antibacterial mechanism by combining the "passive defense" (anti-adhesion) of the borneol unit with the long-chain quaternary ammonium salt (contact sterilization), especially improving the anti-mildew effect and the ability to remove already adhered microorganisms.

[0021] This invention uses borneol-based siloxane and long-chain quaternary ammonium siloxane as raw materials. Both active compounds form covalent bonds with the substrate through siloxane hydrolysis and condensation, resulting in a strong bond, washability, wear resistance, and long service life. The preparation method for the antibacterial and antifungal coating is simple and convenient. By precisely controlling the ratio of borneol-based siloxane to long-chain quaternary ammonium siloxane, the antibacterial and antifungal properties of the coating against specific bacterial species (such as bacteria and fungi) can be optimized to meet the needs of different application scenarios. It is suitable for any substrate material with hydroxyl groups on its surface, such as textiles, paper, plastics, and metal oxides, and has broad prospects in the medical, packaging, and home furnishing fields. Attached Figure Description

[0022] Figure 1 The results are for the bacterial anti-adhesion test of untreated cotton textiles and cotton textiles treated in Example 6, Comparative Example 1, and Comparative Example 2, respectively, where the blank group corresponds to untreated cotton textiles. Figure 2 The results of fungal anti-adhesion tests are given for untreated cotton textiles and cotton textiles treated according to Example 6, Comparative Example 1, and Comparative Example 2, respectively, where the blank group corresponds to untreated cotton textiles. Figure 3 This is a schematic diagram of the reaction path during the preparation of the broad-spectrum long-lasting antibacterial and antifungal coating of the present invention. Detailed Implementation

[0023] This invention provides a broad-spectrum, long-lasting antibacterial and antifungal coating, wherein the broad-spectrum, long-lasting antibacterial and antifungal coating is formed by compounding borneol-based siloxane and long-chain quaternary ammonium salt siloxane on the surface of a substrate, and the borneol-based siloxane has the structure shown in (1): (1)

[0025] R1 is selected from methyl or ethyl; The long-chain quaternary ammonium siloxane has the structure shown in (2): (2)

[0027] Wherein, R2 is selected from methyl or ethyl, and n is selected from an integer between 7 and 17.

[0028] In this invention, the long-chain quaternary ammonium siloxane is preferably dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, tetradecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, dodecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride or octadecyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride.

[0029] In this invention, the surface of the substrate has hydroxyl groups.

[0030] In this invention, the substrate is preferably cotton textiles, paper, plastics, or metal oxides.

[0031] In this invention, the substrate is preferably subjected to surface hydroxylation to obtain hydroxyl groups. The specific process of hydroxylation is as follows: the substrate is immersed in sodium hydroxide solution to obtain a surface-hydroxylated substrate.

[0032] This invention also provides a method for preparing the above-mentioned broad-spectrum long-lasting antibacterial and antifungal coating, comprising the following steps: (1) Mix borneol-based siloxane, long-chain quaternary ammonium salt siloxane and solvent to obtain a mixture; (2) Place the substrate in the mixture and carry out hydrolysis and curing reactions to obtain a broad-spectrum long-lasting antibacterial and antifungal coating.

[0033] In this invention, in step (1), the solvent is a mixed solvent of water and alcohol, wherein the alcohol is methanol and / or isopropanol.

[0034] In this invention, in step (1), the mass ratio of borneol-based siloxane to long-chain quaternary ammonium siloxane is 0.1~1:0.1~1, preferably 1:0.1, 0.9:0.1, 0.8:0.2, 0.7:0.3, 0.6:0.4, 0.5:0.5, 0.4:0.6, or 0.3:0.7; the concentration of borneol-based siloxane in the mixed solution is 2~25 mg / mL, specifically 4 mg / mL, 8 mg / mL, 10 mg / mL, 15 mg / mL, 20 mg / mL, 22.5 mg / mL, or 24 mg / mL.

[0035] In this invention, the mass ratio of the borneol-based siloxane to the area of ​​the substrate is 0.1~1 g: 2500 mm². 2Preferably, the content is 0.3~0.8 g: 2500 mm 2 More preferably, it is 0.4~0.7 g: 2500 mm 2 .

[0036] In this invention, in step (2), the temperature of the hydrolysis reaction is 15~90℃, preferably 25~65℃, more preferably 35~45℃, and the time of the hydrolysis reaction is 1~48 h.

[0037] In this invention, in step (2), the temperature of the curing reaction is 50~200℃, preferably 60~120℃, and more preferably 75~95℃; the curing reaction time is 0.5~1.5 h, preferably 0.8~1.2 h, and more preferably 1 h.

[0038] In this invention, in step (2), the curing reaction includes pre-curing and high-temperature curing; the pre-curing temperature is 70~90℃, preferably 75~85℃, and more preferably 80℃; the pre-curing time is 1~10 min, specifically 2 min, 3 min, 4 min, 6 min, or 8 min; the high-temperature curing temperature is 100~200℃, preferably 110~150℃, and more preferably 120~130℃, and the high-temperature curing time is 1~10 min, specifically 2 min, 3 min, 4 min, 6 min, or 8 min.

[0039] The present invention also provides an application of the above-described broad-spectrum long-lasting antibacterial and antifungal coating in medical devices, food packaging, household or daily necessities.

[0040] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0041] The structural formulas of the borneol-based siloxanes used in Examples 1-14 and Comparative Example 1 are shown below: R1 is a methyl group.

[0042] Example 1

[0043] 0.5 g of sodium hydroxide was mixed with 9.5 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0044] 1 g of borneol siloxane, 0.06667 g of isopropanol, and 0.1 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 15 °C for 48 h to obtain a covalently grafted cotton textile. Finally, the textile was cured at 50 °C for 1.5 h. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the textile.

[0045] Example 2

[0046] 0.5 g of sodium hydroxide was mixed with 9.5 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0047] 0.9 g of borneol siloxane, 0.06667 g of isopropanol, and 0.1 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 20 °C for 24 h to obtain a covalently grafted cotton textile. Finally, the solution was cured at 75 °C for 1 h. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0048] Example 3

[0049] 0.5 g of sodium hydroxide was mixed with 9.5 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0050] 0.8 g of borneol siloxane, 0.1333 g of isopropanol, and 0.2 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 20 °C for 24 h to obtain a covalently grafted cotton textile. Finally, the solution was cured at 75 °C for 0.5 h. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0051] Example 4

[0052] 0.5 g of sodium hydroxide was mixed with 9.5 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0053] 0.7 g of borneol siloxane, 0.2 g of isopropanol, and 0.3 g of dimethyl octadecyl [3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 70 °C for 10 min and then calcined at 100 °C for 10 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0054] Example 5

[0055] 0.5 g of sodium hydroxide was mixed with 25 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0056] 0.6 g of borneol siloxane, 0.2667 g of isopropanol, and 0.4 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain covalently grafted cotton textile. The textile was pre-dried at 70 °C for 8 min and then calcined at 110 °C for 8 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0057] Example 6

[0058] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0059] 0.5 g of borneol siloxane, 0.3333 g of isopropanol, and 0.5 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were added to deionized water to a final volume of 40 mL and mixed thoroughly to obtain a mixture. A cotton textile with a size of 50 mm × 50 mm was immersed in the mixture and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain covalently grafted cotton textile. The textile was pre-dried at 80 °C for 5 min and then calcined at 120 °C for 5 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on its surface.

[0060] Example 7

[0061] 0.5 g of sodium hydroxide was mixed with 25 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0062] 0.4 g of borneol siloxane, 0.4 g of methanol, and 0.6 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 40 °C for 2 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0063] Example 8

[0064] 0.5 g of sodium hydroxide was mixed with 40 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0065] 0.3 g of borneol siloxane, 0.4667 g of methanol, and 0.7 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 40 °C for 2 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 5 min and then calcined at 140 °C for 5 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0066] Example 9

[0067] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0068] 0.2 g of borneol siloxane, 0.5333 g of methanol, and 0.8 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 30 min. Then, a hydrolysis reaction was carried out at 60 °C for 1.5 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 5 min and then calcined at 160 °C for 5 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0069] Example 10

[0070] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0071] 0.1 g of borneol siloxane, 0.6 g of methanol, and 0.9 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 90 °C for 1.5 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 90 °C for 2 min and then calcined at 180 °C for 2 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0072] Example 11

[0073] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0074] 0.1 g of borneol siloxane, 0.6667 g of methanol, and 1 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 90 °C for 1 h to obtain covalently grafted cotton textile. The textile was pre-dried at 90 °C for 1 min and then calcined at 200 °C for 2 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0075] Example 12

[0076] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0077] 0.5 g of borneol siloxane, 0.5 g of methanol, and 0.5 g of octaalkyldimethyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0078] Example 13

[0079] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0080] 0.5 g of borneol siloxane, 0.5 g of methanol, and 0.5 g of dodecyl dimethyl [3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0081] Example 14

[0082] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0083] 0.5 g of borneol siloxane, 0.5 g of methanol, and 0.5 g of tetradecyl dimethyl [3-(trimethoxysilyl)propyl]ammonium chloride were mixed, and deionized water was added to a final volume of 40 mL. The mixture was thoroughly stirred to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm after treatment was immersed in the solution and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain a covalently grafted cotton textile. The textile was pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textile.

[0084] Comparative Example 1

[0085] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0086] 1.0 g of borneol-based siloxane was added to methanol to 40 mL and mixed in a centrifuge tube to obtain a mixture. Cotton textiles with a size of 50 mm × 50 mm after treatment were immersed in the mixture and ultrasonically treated at a frequency of 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain covalently grafted cotton textiles. The textiles were pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textiles were removed, and a broad-spectrum long-lasting antibacterial and antifungal coating was obtained on the surface of the cotton textiles.

[0087] Comparative Example 2

[0088] 0.5 g of sodium hydroxide was mixed with 10 mL of deionized water to obtain a sodium hydroxide solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the sodium hydroxide solution for 12 h. After immersion, it was taken out and rinsed with deionized water to obtain a cotton textile with a hydroxylated surface.

[0089] 0.6667 g of methanol and 1 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride were mixed and water was added to 40 mL to obtain a homogeneous solution. A cotton textile with a size of 50 mm × 50 mm was immersed in the solution and ultrasonically treated at 40 kHz for 40 min. Then, a hydrolysis reaction was carried out at 25 °C for 4 h to obtain covalently grafted cotton textile. The textile was pre-dried at 80 °C for 3 min and then calcined at 120 °C for 3 min. After the reaction was completed, the cotton textile was removed, and a broad-spectrum, long-lasting antibacterial and antifungal coating was obtained on its surface.

[0090] The antibacterial and antifungal coatings obtained in Examples 1-14 and Comparative Examples 1-2 were subjected to anti-adhesion tests against bacteria and fungi, respectively. The strain used was Aspergillus niger. Aspergillus niger (CICC 2364), Staphylococcus aureus Staphylococcus aureus (ATCC 25923), Escherichia coli Escherichia coli (ATCC 25922). "ATCC" refers to the American Type Culture Collection, and "CICC" refers to the China Center of Industrial Culture Collection. Each bacterial strain was used individually as an experimental strain for anti-adhesion testing of the test samples. The malt extract (malt wort) agar medium, tryptic soy agar medium (TSA) for bacterial counting, and tryptic soy liquid medium (TSB) for preparing the bacterial culture were all purchased from Beijing Aoboxing Biotechnology Co., Ltd.

[0091] The test method for anti-adhesion against fungi (Aspergillus niger) is as follows: The test sample is cut into circular pieces with a diameter of 10.0 mm and sterilized by irradiating both sides under a UV lamp for 1 h each. The sterilized circular samples are then flattened onto malt extract (malt juice) agar medium, with the circular sample 1-2 cm from the center of the petri dish. 10 μL of Aspergillus niger spore solution (spore concentration of 5 × 10⁻⁶) is added to the center of the petri dish. 8 The sample was then incubated at a relative humidity of 85 ± 5% and a temperature and humidity of 30℃ for 8 days. After incubation, photographs were taken, and the surface contamination was observed and recorded to evaluate the anti-mold level. The test was considered valid if no mold growth was visible to the naked eye on the sample surface after incubation; otherwise, the test was invalid. The anti-mold level evaluation criteria are shown in Table 1.

[0092] Table 1. Evaluation Criteria for Mildew Resistance Level

[0093] The anti-adhesion test method for bacteria (Staphylococcus aureus, Escherichia coli) is as follows: A bacterial concentration of 10 is prepared using phosphate buffer. 7CFU / mL bacterial suspension. Circular cotton textile samples (10 mm in diameter) were immersed in 1 mL of bacterial suspension and co-cultured at 37°C for 24 h. After incubation, the samples were removed, washed three times with sterile physiological saline, and the washing solution was removed with filter paper. They were then placed in 2 mL of sterile physiological saline and sonicated at 40 kHz for 15 min. 100 μL of the treatment solution was plated on TSA solid medium and incubated at 37°C for 24 h. The number of colonies grown on the plates was counted. Untreated samples served as a blank control group. The anti-adhesion rate was calculated using the formula R = [(AB) / A] × 100%, where R is the anti-adhesion rate (%), A is the number of bacteria adhering to the surface of the untreated sample (CFU / mL), and B is the number of bacteria adhering to the surface of the treated sample (CFU / mL). The test results for anti-mildew grade and anti-adhesion are shown in Table 2. Table 2 Results of Anti-mildew Rating and Anti-adhesion Tests

[0094] Figure 1 The results are for the anti-adhesion test of untreated cotton textiles and cotton textiles treated in Example 6, Comparative Example 1, and Comparative Example 2, respectively, with the blank group being untreated cotton textiles. Figure 2 The results show the anti-adhesion properties of untreated cotton textiles and cotton textiles treated according to Example 6, Comparative Example 1, and Comparative Example 2, respectively, against fungi. The blank group consisted of untreated cotton textiles. Figure 1 , 2 As can be seen, the antibacterial and antifungal coating obtained by modifying borneol-based siloxane and long-chain quaternary ammonium salt siloxane in Example 6 not only exhibits good bactericidal effect, but also has anti-adhesion ability on its surface, and its antifungal performance also achieves ideal results. When the ratio of the two is within a certain range, the surface of cotton textiles has both anti-adhesion and bactericidal ability, and its antifungal performance is better, which is significantly improved compared with Comparative Example 2.

[0095] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A broad spectrum long lasting antimicrobial and mildew resistant coating characterized in that, The broad-spectrum long-acting antibacterial and mildew-proof coating is formed on the surface of a substrate by compounding borneol-based siloxane and long-chain quaternary ammonium salt siloxane, wherein the borneol-based siloxane has the structure as shown in (1): （1） wherein R1 is selected from methyl or ethyl; The long-chain quaternary ammonium salt siloxane has the structure as shown in (2): （2） wherein R2 is selected from methyl or ethyl, and n is an integer between 7 and 17.

2. The broad spectrum long lasting antimicrobial mold resistant coating according to claim 1, wherein, The surface of the substrate has hydroxyl groups.

3. A process for the preparation of a broad spectrum long lasting antimicrobial mold resistant coating as claimed in claim 1 or 2, characterized in that, The method comprises the following steps: (1) mixing borneol-based siloxane, long-chain quaternary ammonium salt siloxane and a solvent to obtain a mixed solution; (2) placing the substrate in the mixed solution to perform hydrolysis reaction and curing reaction, thereby obtaining the broad-spectrum long-acting antibacterial and mildew-proof coating.

4. The method of claim 3, wherein the broad-spectrum long-acting antimicrobial and mildew-proof coating is prepared by adding 0.1 to 0.5 parts by weight of the compound of formula 1 to 100 parts by weight of the base material. In step (1), the solvent is a mixed solvent of water and an alcohol compound, wherein the alcohol compound is methanol and / or isopropyl alcohol.

5. The method for preparing the broad-spectrum, long-lasting antibacterial and antifungal coating according to claim 3 or 4, characterized in that, In step (1), the mass ratio of the borneol-based siloxane and the long-chain quaternary ammonium salt siloxane is 0.1-1:0.1-1, and the concentration of the borneol-based siloxane in the mixed solution is 2-25 mg / mL.

6. The method for preparing the broad-spectrum, long-lasting antibacterial and antifungal coating according to claim 5, characterized in that, The mass of the borneol-based siloxane to the area of the substrate is 0.1 to 1 g: 2500 mm 2 .

7. The method of making a broad spectrum long lasting antimicrobial mold resistant coating according to claim 3 or 4 or 6, wherein, In step (2), the temperature of the hydrolysis reaction is 15-90℃, and the time of the hydrolysis reaction is 1-48 h.

8. The method for preparing the broad-spectrum, long-lasting antibacterial and antifungal coating according to claim 7, characterized in that, In step (2), the temperature of the curing reaction is 50-200℃, and the time of the curing reaction is 0.5-1.5 h.

9. The method for preparing the broad-spectrum, long-lasting antibacterial and antifungal coating according to claim 7, characterized in that, In step (2), the curing reaction comprises pre-curing and high-temperature curing; the temperature of the pre-curing is 70-90℃, and the time of the pre-curing is 1-10 min; the temperature of the high-temperature curing is 100-200℃, and the time of the high-temperature curing is 1-10 min.

10. The broad-spectrum long-acting antibacterial and mildew-proof coating according to claim 1 or 2 is applied to medical devices, food packaging, household or daily necessities.

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