Antibacterial and mildew-proof wood wax oil and preparation method thereof

Abstract

The application relates to an antibacterial and mildew-proof wood wax oil and a preparation method thereof, and relates to the technical field of coatings, which is prepared from the following raw materials in parts of mass: 30-40 parts of castor oil-based hyperbranched UV curing polyurethane acrylate, 10-20 parts of epoxy soybean oil, 8-12 parts of composite plant wax, 0.8-1.2 parts of a photoinitiator, 0.5-1 part of guanidine acetate, 5-8 parts of chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1-3 parts of tea polyphenol modified montmorillonite, 2-4 parts of 2,4-diamino-6-vinyl-S-triazine, 0.1-0.3 parts of a skinning inhibitor, 0.1-0.3 parts of a defoaming agent, 0.1-0.6 parts of a drier, and 15-30 parts of a diluent. The antibacterial and mildew-proof wood wax oil has remarkable antibacterial and mildew-proof effects and large adhesion.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to an antibacterial and mildew-resistant wood wax oil and its preparation method. Background Technology

[0002] Wood wax oil is an environmentally friendly wood coating made primarily from natural plant oils and waxes. It offers advantages such as breathability, moisture resistance, and protection of wood grain, and is widely used in solid wood furniture, flooring, and outdoor landscaping. However, traditional wood wax oils have poor antibacterial and anti-mold properties. In humid environments (such as the rainy season in southern China, bathrooms, and kitchens), mold (such as Aspergillus niger and Penicillium) and bacteria (such as Escherichia coli and Staphylococcus aureus) easily grow on the wood surface, leading to discoloration, performance degradation, and even potential health risks.

[0003] To address this issue, existing technologies typically add antibacterial agents to wood wax oils, such as organic antibacterial agents (e.g., isothiazolinone) or inorganic antibacterial agents (e.g., nano-silver). However, organic antibacterial agents suffer from volatility and short-lasting antibacterial effects; while nano-silver offers good antibacterial efficacy, it is expensive, prone to leaching, and its heavy metal ions pose potential hazards to the environment and human health. Furthermore, existing antibacterial wood wax oils also suffer from uneven antibacterial agent dispersion and impaired film-forming properties (e.g., slow drying speed and poor adhesion), limiting their practical application.

[0004] To address the aforementioned issues, Chinese invention patent CN108676494B discloses an antibacterial wood wax oil for wood products and its preparation method. This method uses natural plant oils and natural plant waxes as main raw materials, and adds other additives under an inert atmosphere to ultimately synthesize an antibacterial wood wax oil for wood products. This invention is the first to apply nano-silver dispersion to the preparation of wood wax oil, which can give the wood wax oil better performance and antibacterial ability, making it applicable to the coatings field. However, its anti-mildew effect still needs further improvement. In addition, the use of nano-silver makes this wood wax oil more expensive.

[0005] Therefore, developing a wood wax oil with long-lasting antibacterial and antifungal effects, environmental safety, and excellent physical properties has become a research hotspot in the field of wood coatings. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide an antibacterial and antifungal wood wax oil with significant antibacterial and antifungal effects and strong adhesion, as well as its preparation method.

[0007] To achieve the above objectives, the technical solution adopted by this invention is as follows: an antibacterial and mildew-resistant wood wax oil, which, by weight, is made from the following raw materials: 30-40 parts of castor oil-based hyperbranched UV-cured polyurethane acrylate, 10-20 parts of epoxidized soybean oil, 8-12 parts of composite plant wax, 0.8-1.2 parts of photoinitiator, 0.5-1 parts of guanidine acetate, 5-8 parts of chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1-3 parts of tea polyphenol-modified montmorillonite, 2-4 parts of 2,4-diamino-6-vinyl-S-triazine, 0.1-0.3 parts of anti-skinning agent, 0.1-0.3 parts of defoamer, 0.1-0.6 parts of drying agent, and 15-30 parts of diluent.

[0008] Preferably, there are no special requirements for the source of the castor oil-based hyperbranched UV-curable polyurethane acrylate. In one embodiment of the present invention, the castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B.

[0009] Preferably, the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.

[0010] Preferably, the composite plant wax is made by compounding carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:(0.8-1.2):1.

[0011] Preferably, the photoinitiator is benzoin ether.

[0012] Preferably, the preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, and stirring and reacting at 48-52℃ for 5-7 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent.

[0013] Preferably, the chitosan quaternary ammonium salt has a molecular weight of 100,000 and a degree of substitution of 80%.

[0014] Preferably, the acetic acid solution has a mass percentage concentration of 1%-3%.

[0015] Preferably, the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano titanium dioxide is 2:100:3.

[0016] Preferably, the particle size of the nano-titanium dioxide is 10-80 nm.

[0017] Preferably, the preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 340-360°C at a heating rate of 3-5°C / min, and calcining it at a constant temperature for 2-3 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 4-6%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 58-62°C, and reacting it for 4-6 hours at a stirring speed of 380-420 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then drying it in a vacuum drying oven at 58-62°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite.

[0018] Preferably, the particle size of the montmorillonite powder is 100-200 mesh.

[0019] Preferably, the volume ratio of ethanol to deionized water is 1:4.

[0020] Preferably, the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0021] Preferably, the anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicone defoamer BYK-141.

[0022] Preferably, the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0023] Another objective of this invention is to provide a method for preparing the aforementioned antibacterial and mildew-resistant wood wax oil, comprising the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 120-140°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 1-2 hours; cooling to 80-90°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 1-2 hours; then cooling to 60°C, adding other raw materials, stirring for 0.5-1 hour, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0024] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0025] (1) The preparation method of antibacterial and mildew-resistant wood wax oil disclosed in this invention is simple, easy to operate, has high preparation efficiency and high finished product qualification rate, low dependence on equipment, suitable for continuous large-scale production, and has high promotion and application value.

[0026] (2) The antibacterial and mildew-resistant wood wax oil disclosed in this invention is made from the following raw materials by weight: 30-40 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 10-20 parts epoxidized soybean oil, 8-12 parts composite plant wax, 0.8-1.2 parts photoinitiator, 0.5-1 parts guanidine acetate, 5-8 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1-3 parts tea polyphenol-modified montmorillonite, 2-4 parts 2,4-diamino-6-vinyl-S-triazine, 0.1-0.3 parts anti-skinning agent, 0.1-0.3 parts defoamer, 0.1-0.6 parts drying agent, and 15-30 parts diluent. Through the synergistic effect of the raw materials, the finished product has a long-lasting antibacterial and mildew-resistant effect, is environmentally friendly and safe, and has strong adhesion. This formula achieves multi-dimensional innovation in raw material selection, breaking through the limitations of traditional wood wax oil which is mainly composed of single plant oils and ordinary waxes. This invention introduces castor oil-based hyperbranched UV-curable polyurethane acrylate as the main film-forming material. Its hyperbranched structure endows the molecules with excellent fluidity and compatibility. When compounded with epoxidized soybean oil, the resulting cross-linked network retains the natural and environmentally friendly properties of plant oils while significantly improving the curing speed and cross-linking density of the coating through the UV curing mechanism, thus solving the pain points of slow drying and insufficient hardness of traditional wood wax oils. The composite plant wax works synergistically with the above film-forming system, and the dosage range of 8-12 parts has been precisely optimized to ensure a smooth surface texture of the coating while avoiding the problem of decreased adhesion caused by excessive wax. This is significantly different from the existing technology that relies solely on plant wax to adjust hardness.

[0027] (3) The antibacterial and mildew-resistant wood wax oil disclosed in this invention constructs a triple antibacterial and mildew-resistant system of "organic antibacterial agent + composite nano antibacterial agent + natural modified mineral", which has outstanding inventiveness. Guanidine acetate, as a highly efficient organic antibacterial component, can quickly destroy the cell membrane of microorganisms; the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent forms a synergistic effect through the cationic adsorption of chitosan quaternary ammonium salt and the photocatalytic oxidation of nano TiO2, which significantly broadens the antibacterial spectrum compared with single antibacterial agents; the tea polyphenol modified montmorillonite not only relies on the physical barrier effect of montmorillonite, but its loaded tea polyphenols can also enhance the long-term effect through the oxidative antibacterial effect of phenolic hydroxyl groups. The amino and vinyl groups in the 2,4-diamino-6-vinyl-S-triazine molecule can react chemically with other components and anchor in the coating network, which not only avoids the migration and loss of antibacterial components, but also specifically inhibits the germination of mold spores, complementing the above-mentioned antibacterial components and making the antibacterial and mildew-resistant effects more obvious.

[0028] (4) The antibacterial and mildew-resistant wood wax oil disclosed in this invention combines castor oil-based hyperbranched UV-curable polyurethane acrylate with a photoinitiator, which enables the coating to be initially cured in 3-5 minutes under UV irradiation, significantly improving the drying speed. The layered structure of tea polyphenol-modified montmorillonite forms a "maze effect" in the coating, which, combined with the flexibility of epoxidized soybean oil, makes the coating more flexible and solves the performance contradiction of traditional wood wax oil that is "hard and brittle, soft and soft".

[0029] (5) The antibacterial and mildew-resistant wood wax oil disclosed in this invention ensures high performance while strictly controlling the content of harmful substances. All raw materials are free of volatile organic compounds such as formaldehyde and benzene series. Components such as guanidine acetate and tea polyphenols are derived from natural or biodegradable sources, meeting the latest environmental protection standards. The dosage of additives such as anti-skinning agents and defoamers is controlled in the low range of 0.1-0.3 parts, achieving high efficiency through intermolecular forces with the main components, avoiding performance degradation caused by excessive additives, which is more environmentally friendly than the existing technology that relies on high additive dosages. In addition, the dosage of 15-30 parts of diluent is precisely matched, ensuring workability while reducing volatile emissions, thus balancing production practicality and environmental friendliness. Detailed Implementation

[0030] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0031] Example 1

[0032] An antibacterial and mildew-resistant wood wax oil, by weight, is made from the following raw materials: 30 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 10 parts epoxidized soybean oil, 8 parts composite plant wax, 0.8 parts photoinitiator, 0.5 parts guanidine acetate, 5 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1 part tea polyphenol modified montmorillonite, 2 parts 2,4-diamino-6-vinyl-S-triazine, 0.1 parts anti-skinning agent, 0.1 parts defoamer, 0.1 parts drying agent, and 15 parts diluent.

[0033] The castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B; the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the composite plant wax is composed of carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:0.8:1; and the photoinitiator is benzoin ether.

[0034] The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, stirring and reacting at 48°C for 5 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent; wherein the molecular weight of the chitosan quaternary ammonium salt is 100,000 and the degree of substitution is 80%; the mass percentage concentration of the acetic acid solution is 1%; the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; and the particle size of the nano-titanium dioxide is 10 nm.

[0035] The preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 340°C at a heating rate of 3°C / min, and calcining it at a constant temperature for 2 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 4%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 58°C, and reacting it for 4 hours at a stirring speed of 380 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then drying it in a vacuum drying oven at 58°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite; the particle size of the montmorillonite powder is 100 mesh; the volume ratio of ethanol to deionized water is 1:4; and the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0036] The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0037] A method for preparing the antibacterial and mildew-resistant wood wax oil includes the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 120°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 1 hour; cooling to 80°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 1 hour; then cooling to 60°C, adding other raw materials, stirring for 0.5 hours, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0038] Example 2

[0039] An antibacterial and mildew-resistant wood wax oil, by weight, is made from the following raw materials: 33 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 12 parts epoxidized soybean oil, 9 parts composite plant wax, 0.9 parts photoinitiator, 0.6 parts guanidine acetate, 6 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1.5 parts tea polyphenol-modified montmorillonite, 2.5 parts 2,4-diamino-6-vinyl-S-triazine, 0.15 parts anti-skinning agent, 0.15 parts defoamer, 0.2 parts drying agent, and 17 parts diluent.

[0040] The castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B; the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the composite plant wax is composed of carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:0.9:1; and the photoinitiator is benzoin ether.

[0041] The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, and stirring and reacting at 49°C for 5.5 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent; wherein the molecular weight of the chitosan quaternary ammonium salt is 100,000 and the degree of substitution is 80%; the mass percentage concentration of the acetic acid solution is 1.5%; the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; and the particle size of the nano-titanium dioxide is 30 nm.

[0042] The preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 345°C at a heating rate of 3.5°C / min, then calcining it at a constant temperature for 2.3 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 4.5%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 59°C, and reacting it for 4.5 hours at a stirring speed of 390 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then drying it in a vacuum drying oven at 59°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite; the particle size of the montmorillonite powder is 130 mesh; the volume ratio of ethanol to deionized water is 1:4; and the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0043] The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0044] A method for preparing the antibacterial and mildew-resistant wood wax oil includes the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 125°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 1.2 hours; cooling to 83°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 1.2 hours; then cooling to 60°C, adding other raw materials, stirring for 0.7 hours, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0045] Example 3

[0046] An antibacterial and mildew-resistant wood wax oil, by weight, is made from the following raw materials: 35 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 15 parts epoxidized soybean oil, 10 parts composite plant wax, 1 part photoinitiator, 0.7 parts guanidine acetate, 6.5 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 2 parts tea polyphenol modified montmorillonite, 3 parts 2,4-diamino-6-vinyl-S-triazine, 0.2 parts anti-skinning agent, 0.2 parts defoamer, 0.4 parts drying agent, and 22 parts diluent.

[0047] The castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B; the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the composite plant wax is composed of carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:1:1; and the photoinitiator is benzoin ether.

[0048] The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, stirring and reacting at 50°C for 6 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent; wherein the molecular weight of the chitosan quaternary ammonium salt is 100,000 and the degree of substitution is 80%; the mass percentage concentration of the acetic acid solution is 2%; the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; and the particle size of the nano-titanium dioxide is 10-80 nm.

[0049] The preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 350°C at a heating rate of 4°C / min, and calcining it at a constant temperature for 2.5 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 5%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 60°C, and reacting it for 5 hours at a stirring speed of 400 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then drying it in a vacuum drying oven at 60°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite; the particle size of the montmorillonite powder is 150 mesh; the volume ratio of ethanol to deionized water is 1:4; and the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0050] The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0051] A method for preparing the antibacterial and mildew-resistant wood wax oil includes the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 130°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 1.5 hours; cooling to 85°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 1.5 hours; then cooling to 60°C, adding other raw materials, stirring for 0.75 hours, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0052] Example 4

[0053] An antibacterial and mildew-resistant wood wax oil, by weight, is made from the following raw materials: 38 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 18 parts epoxidized soybean oil, 11 parts composite plant wax, 1.1 parts photoinitiator, 0.9 parts guanidine acetate, 7.5 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 2.5 parts tea polyphenol-modified montmorillonite, 3.5 parts 2,4-diamino-6-vinyl-S-triazine, 0.25 parts anti-skinning agent, 0.25 parts defoamer, 0.5 parts drying agent, and 28 parts diluent.

[0054] The castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B; the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the composite plant wax is compounded from carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:1.1:1; and the photoinitiator is benzoin ether.

[0055] The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, and stirring and reacting at 51°C for 6.5 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent; wherein the molecular weight of the chitosan quaternary ammonium salt is 100,000 and the degree of substitution is 80%; the mass percentage concentration of the acetic acid solution is 2.5%; the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; and the particle size of the nano-titanium dioxide is 50 nm.

[0056] The preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 355°C at a heating rate of 4.5°C / min, then calcining it at a constant temperature for 2.8 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 5.5%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 61°C, and reacting it for 5.5 hours at a stirring speed of 410 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then drying it in a vacuum drying oven at 61°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite; the particle size of the montmorillonite powder is 180 mesh; the volume ratio of ethanol to deionized water is 1:4; and the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0057] The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0058] A method for preparing the antibacterial and mildew-resistant wood wax oil includes the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 135°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 1.8 hours; cooling to 88°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 1.8 hours; then cooling to 60°C, adding other raw materials, stirring for 0.9 hours, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0059] Example 5

[0060] An antibacterial and mildew-resistant wood wax oil, by weight, is made from the following raw materials: 40 parts castor oil-based hyperbranched UV-cured polyurethane acrylate, 20 parts epoxidized soybean oil, 12 parts composite plant wax, 1.2 parts photoinitiator, 1 part guanidine acetate, 8 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 3 parts tea polyphenol modified montmorillonite, 4 parts 2,4-diamino-6-vinyl-S-triazine, 0.3 parts anti-skinning agent, 0.3 parts defoamer, 0.6 parts drying agent, and 30 parts diluent.

[0061] The castor oil-based hyperbranched UV-curable polyurethane acrylate is prepared according to the method of Example 1 of Chinese Invention Patent No. CN106397719B; the epoxidized soybean oil is epoxidized soybean oil E107074, provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the composite plant wax is composed of carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:1.2:1; and the photoinitiator is benzoin ether.

[0062] The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, stirring and reacting at 52°C for 7 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent; wherein the molecular weight of the chitosan quaternary ammonium salt is 100,000 and the degree of substitution is 80%; the mass percentage concentration of the acetic acid solution is 3%; the mass ratio of the chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; and the particle size of the nano-titanium dioxide is 10-80 nm.

[0063] The preparation method of the tea polyphenol-modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace and heating it to 360°C at a heating rate of 5°C / min, and calcining it at a constant temperature for 3 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 6%; subsequently, adding ethanol and stirring for another hour to obtain a montmorillonite suspension; slowly adding tea polyphenols to the montmorillonite suspension, heating it to 62°C, and reacting it for 6 hours at a stirring speed of 420 r / min; after the reaction, centrifuging and repeatedly washing with deionized water until no free tea polyphenols are detected in the washing liquid; then placing it in a vacuum drying oven and drying it at 62°C to constant weight; the dried product is pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite; the particle size of the montmorillonite powder is 180 mesh; the volume ratio of ethanol to deionized water is 1:4; and the mass ratio of tea polyphenols to montmorillonite powder is 1:5.

[0064] The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

[0065] A method for preparing the antibacterial and mildew-resistant wood wax oil includes the following steps: adding epoxidized soybean oil and composite plant wax to a reaction vessel, heating to 140°C, stirring until completely melted and mixed evenly, and maintaining the temperature and stirring for 2 hours; cooling to 90°C, adding chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite, and continuing to stir for 2 hours; then cooling to 60°C, adding other raw materials, stirring for 1 hour, cooling to room temperature, and filtering to obtain the antibacterial and mildew-resistant wood wax oil.

[0066] Comparative Example 1

[0067] This example is basically the same as Example 1, except that guanidine acetate was not added, and an equal amount of montmorillonite was used instead of tea polyphenol-modified montmorillonite.

[0068] Comparative Example 2

[0069] This example is basically the same as Example 1, except that 2,4-diamino-6-vinyl-S-triazine was not added, and an equal amount of castor oil was used instead of castor oil-based hyperbranched UV-cured polyurethane acrylate.

[0070] The following test methods were used to conduct relevant performance tests on each product. The curing conditions during the test were: reaction for 25 minutes under ultraviolet light irradiation with a wavelength of 365nm and a light intensity of 100mW / cm. The test results are shown in Table 1.

[0071] (1) Antibacterial properties and durability: Tested according to GB / T 21866-2008 "Determination of antibacterial properties and antibacterial effects of antibacterial coatings (films)";

[0072] (2) Anti-mildew rating: Tested according to GB / T 1741-2007 "Test Method for Anti-mildew Resistance of Paint Film", the tested mold is Aspergillus niger (CGMCC 3.5487);

[0073] (3) Adhesion rating: Tested according to GB / T 9286-2021 "Paints and Varnishes Cross-cut Test".

[0074] Table 1. Test results of antibacterial and antifungal properties of wood wax oil

[0075]

[0076] As can be seen from Table 1, the antibacterial and antifungal wood wax oil products prepared in each embodiment of the present invention have better antibacterial and antifungal properties than the comparative example, and their adhesion is also better. The combined addition of guanidine acetate, tea polyphenol modified montmorillonite, 2,4-diamino-6-vinyl-S-triazine and castor oil-based hyperbranched UV-curable polyurethane acrylate is beneficial to improving the above properties.

[0077] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. An antibacterial and mildew-resistant wood wax oil, characterized in that, The product is made from the following raw materials by weight: 30-40 parts castor oil-based hyperbranched UV-curable polyurethane acrylate, 10-20 parts epoxidized soybean oil, 8-12 parts composite plant wax, 0.8-1.2 parts photoinitiator, 0.5-1 part guanidine acetate, 5-8 parts chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent, 1-3 parts tea polyphenol modified montmorillonite, 2-4 parts 2,4-diamino-6-vinyl-S-triazine, 0.1-0.3 parts anti-skinning agent, 0.1-0.3 parts defoamer, 0.1-0.6 parts drying agent, and 15-30 parts diluent.

2. The antibacterial and mildew-resistant wood wax oil according to claim 1, characterized in that, The composite plant wax is made by blending carnauba wax, beeswax, and candelilla wax in a mass ratio of 2:(0.8-1.2):

1.

3. The antibacterial and mildew-resistant wood wax oil according to claim 1, characterized in that, The photoinitiator is benzoin ether.

4. The antibacterial and mildew-resistant wood wax oil according to claim 1, characterized in that, The preparation method of the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent includes the following steps: dissolving chitosan quaternary ammonium salt in acetic acid solution; dispersing nano-titanium dioxide in deionized water to prepare a nano-titanium dioxide dispersion with a mass fraction of 3%; then slowly adding the nano-titanium dioxide dispersion to the chitosan quaternary ammonium salt solution, and stirring and reacting at 48-52℃ for 5-7 hours to obtain the chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent.

5. The antibacterial and mildew-resistant wood wax oil according to claim 4, characterized in that, The chitosan quaternary ammonium salt has a molecular weight of 100,000 and a degree of substitution of 80%; the acetic acid solution has a mass percentage concentration of 1%-3%.

6. The antibacterial and mildew-resistant wood wax oil according to claim 4, characterized in that, The mass ratio of chitosan quaternary ammonium salt, acetic acid solution, and nano-titanium dioxide is 2:100:3; the particle size of the nano-titanium dioxide is 10-80 nm.

7. The antibacterial and mildew-resistant wood wax oil according to claim 1, characterized in that, The preparation method of the tea polyphenol modified montmorillonite includes the following steps: placing montmorillonite powder in a muffle furnace, heating it to 340-360℃ at a heating rate of 3-5℃ / min, and calcining it at a constant temperature for 2-3 hours; then adding it to deionized water to prepare a suspension with a mass fraction of 4-6%; Subsequently, ethanol was added, and stirring was continued for 1 hour to obtain a montmorillonite suspension. Tea polyphenols were slowly added to the montmorillonite suspension, and the temperature was raised to 58-62℃. The mixture was stirred at a speed of 380-420 r / min for 4-6 hours. After the reaction was completed, the mixture was centrifuged and repeatedly washed with deionized water until no free tea polyphenols were detected in the washing liquid. The mixture was then placed in a vacuum drying oven and dried at 58-62℃ to constant weight. The dried product was pulverized by a pulverizer and then passed through a 100-mesh sieve to obtain tea polyphenol-modified montmorillonite.

8. The antibacterial and mildew-resistant wood wax oil according to claim 7, characterized in that, The particle size of the montmorillonite powder is 100-200 mesh; the volume ratio of the ethanol to the deionized water is 1:4; and the mass ratio of the tea polyphenols to the montmorillonite powder is 1:

5.

9. The antibacterial and mildew-resistant wood wax oil according to claim 1, characterized in that, The anti-skinning agent is methyl ethyl ketone oxime; the defoamer is organosilicon defoamer BYK-141; the drying agent is cobalt isooctanoate; and the diluent is turpentine oil.

10. A method for preparing an antibacterial and mildew-resistant wood wax oil according to any one of claims 1-9, characterized in that, The process includes the following steps: Epoxidized soybean oil and composite plant wax are added to a reaction vessel, heated to 120-140℃, stirred until completely melted and mixed evenly, and kept warm and stirred for 1-2 hours; the temperature is lowered to 80-90℃, chitosan quaternary ammonium salt-nano TiO2 composite antibacterial agent and tea polyphenol modified montmorillonite are added, and stirring is continued for 1-2 hours; then the temperature is lowered to 60℃, other raw materials are added, stirred for 0.5-1 hour, cooled to room temperature, and filtered to obtain antibacterial and mildew-resistant wood wax oil.

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