Aerogel type antibacterial and mildew-proof agent and preparation method and application thereof

Abstract

The present disclosure provides an aerogel-type antibacterial and mildew-proof agent and its preparation method and application, which belongs to the technical field of antibacterial and mildew-proof agents. The aerogel-type antibacterial and mildew-proof agent disclosed herein includes the following components in parts by weight: 15-30 parts of zirconium dioxide aerogel, 10-20 parts of antibacterial and mildew-proof agent, and 0.1-0.5 parts of coating agent; wherein the antibacterial and mildew-proof agent is at least three of polyhexamethylene biguanide, benzalkonium chloride, benzalkonium bromide, chlorphenesin, cetylpyridinium chloride, cetrimide bromide, benzethonium chloride, chlorhexidine glucose, and dimethyl ammonium chloride; the coating agent is hydrophilic wax powder. The antibacterial and mildew-proof plastic prepared by the aerogel-type antibacterial and mildew-proof agent disclosed herein has the advantages of good killing effect on bacteria and fungi, high light transmittance, and low yellowing.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial and mildew-proofing agents, and in particular to an aerogel-type antibacterial and mildew-proofing agent and a preparation method and application thereof. Background Art

[0002] Plastics are easily contaminated and breed a variety of microorganisms during processing and use, causing pathogenic bacteria, molds, etc. to cause certain harm to people's health. In recent years, with the improvement of people's living standards and the enhancement of hygiene awareness, people have paid more and more attention to the pursuit of a healthy living environment, and the demand for antibacterial materials and products has increased day by day, among which antibacterial and mildew-proof plastic products occupy an important position. Due to the wide variety of thermoplastics, easy processing and wide range of applications, they have been widely used in various plastic products in daily life, such as household appliances, daily necessities, sanitary ware, decorative materials and other fields. Research and development of antibacterial and mildew-proof thermoplastic products can make the products have hygienic self-cleaning functions. Compared with conventional chemical and physical disinfection methods, they have the characteristics of long time, economy and convenience, so they have become one of the hot spots in the research of antibacterial and mildew-proof plastics.

[0003] The preparation of antibacterial and mildew-proof plastics mainly involves uniformly mixing the base resin, antibacterial and mildew-proof agent and process additives in a certain proportion, then directly melt blending to prepare a modified resin with antibacterial and mildew-proof functions, and finally manufacturing various antibacterial and mildew-proof products through various plastic molding processing methods (such as extrusion, injection molding, casting, blow molding, blister molding, etc.). At present, the antibacterial and mildew-proof agents used in the market mainly include two categories: inorganic and organic antibacterial and mildew-proof agents. Among them, inorganic antibacterial and mildew-proof agents are mainly inorganic substances that carry antibacterial metal ions (such as one or more of silver ions, zinc ions, copper ions, etc.), and there are many types of carriers that can be used for loading, including zeolite (natural or synthetic zeolite), zirconium phosphate, soluble glass, calcium phosphate, silica gel, etc. Organic antibacterial and mildew-proof agents are divided into quaternary ammonium salts, quaternary phosphonium salts, imidazoles, pyridines, organic metals, etc. according to their structures. Inorganic antibacterial and mildew-proof agents have the characteristics of high safety, good heat resistance, and long-lasting mildew resistance. However, their antibacterial and mildew-proof properties are not immediate and their antibacterial and mildew-proof effects are lower than those of organic antibacterial and mildew-proof agents. In addition, the use of precious metals results in higher prices. Organic antibacterial and mildew-proof agents have the advantages of high killing rate and fast killing speed against bacteria and fungi, as well as a wide range of applications. However, organic antibacterial and mildew-proof agents have poor heat resistance. After high-temperature processing, organic antibacterial and mildew-proof agents decompose, resulting in a decrease in the antibacterial and mildew-proof effect and light transmittance of the resulting plastics, and an increase in yellowing. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an aerogel-type antibacterial and mildew-proof agent and its preparation method and application. The antibacterial and mildew-proof plastic prepared by the aerogel-type antibacterial and mildew-proof agent of the present invention has the advantages of antibacterial and mildew-proof effect, high light transmittance, and low yellowing.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present disclosure is as follows: In the first aspect, an aerogel-type antibacterial and antifungal agent is provided, comprising the following components in parts by weight: 15-30 parts of zirconium dioxide aerogel, 10-20 parts of antibacterial and antifungal agent, and 0.1-0.5 parts of coating agent;

[0006] Among them, the antibacterial and antifungal agents are at least three of polyhexamethylene biguanide, benzalkonium chloride (bromide), chlorphenesin, cetylpyridinium chloride, cetrimide bromide, benzethonium chloride, chlorhexidine gluconate, and dimethylammonium chloride; the coating agent is hydrophilic wax powder.

[0007] In some embodiments, the zirconium dioxide aerogel has an average porosity of 80-99.8%, an average pore size of 10-40 nm, and an average particle size of 100-150 nm.

[0008] In some embodiments, the average particle size of the hydrophilic wax powder is 100-150 nm.

[0009] In a second aspect, a method for preparing the aerogel-type antibacterial and antifungal agent is provided, comprising the following steps:

[0010] After the zirconium dioxide aerogel and the antibacterial and mildew-proof agent aqueous solution are uniformly mixed, a coating agent is added to carry out a first reaction, and the obtained product is dried to obtain an aerogel type antibacterial and mildew-proof agent; wherein the pH value of the antibacterial and mildew-proof agent aqueous solution is 5-7.

[0011] In some embodiments, based on 100 parts by weight of the antibacterial and mildew-proofing agent aqueous solution, the amount of the antibacterial and mildew-proofing agent is 10-20 parts by weight.

[0012] In some embodiments, the temperature of the first reaction is 50-70°C and the time is 30-40 min;

[0013] In some embodiments, the uniform mixing is carried out by ultrasound.

[0014] In some embodiments, the ultrasound has a power of 480-800 W and a duration of 15-25 min.

[0015] In some embodiments, the method for preparing the zirconium dioxide aerogel comprises the following steps:

[0016] Dissolving the zirconium source in the template aqueous solution, then adding the acidifier, and stirring evenly to obtain a first solution;

[0017] adding an acid binding agent to the first solution for neutralization reaction to obtain a zirconium salt sol;

[0018] The zirconium salt sol is subjected to a second reaction and dried to obtain zirconium dioxide aerogel.

[0019] In some embodiments, the zirconium source is at least one of zirconium oxide, zirconium nitrate, zirconium oxynitrate, zirconium oxychloride, zirconium sulfate, zirconium oxysulfate, and zirconium acetate.

[0020] In some embodiments, the acid binding agent is at least one of propylene oxide, urea, and ammonia water.

[0021] In some embodiments, the acid regulator is at least one of hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, acetic acid, and citric acid.

[0022] In some embodiments, based on 100 parts by weight of the zirconium salt sol, the zirconium source is 1-3 parts by weight, and the template is 3-6 parts by weight;

[0023] In some embodiments, the molar ratio of hydrogen ions in the acid binding agent and the acid regulating agent is 2-20;

[0024] In some embodiments, the mass ratio of the antibacterial and mildew-proofing agent aqueous solution to the coating agent is 1000:1-5;

[0025] In some embodiments, the temperature of the second reaction is 60-80° C., and the time is 4-12 hours.

[0026] In a third aspect, provided is the use of the aerogel-type antibacterial and mildew-proofing agent or the aerogel-type antibacterial and mildew-proofing agent prepared by the preparation method of the aerogel-type antibacterial and mildew-proofing agent in plastics.

[0027] In a fourth aspect, an antibacterial and mildew-proof plastic is provided, wherein the antibacterial and mildew-proof plastic comprises the aerogel-type antibacterial and mildew-proof agent or an aerogel-type antibacterial and mildew-proof agent prepared by the preparation method of the aerogel-type antibacterial and mildew-proof agent.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) In the aerogel-type antibacterial and mildew-proof agent disclosed in the present invention, zirconium dioxide aerogel is used as a carrier. The zirconium dioxide aerogel has a porous structure, which allows the antibacterial and mildew-proof agent to enter the pores of the zirconium dioxide aerogel, and the coating agent is wrapped around the surface of the zirconium dioxide aerogel and the antibacterial and mildew-proof agent to form a protective film. During the high-temperature processing of the aerogel-type antibacterial and mildew-proof agent and the matrix resin, the zirconium dioxide aerogel and the coating agent melt, absorb the heat on the surface of the antibacterial and mildew-proof agent, make the temperature near the antibacterial and mildew-proof agent lower than the boiling point of the antibacterial and mildew-proof agent, inhibit the decomposition of the antibacterial and mildew-proof agent, and improve the high temperature resistance of the antibacterial and mildew-proof agent, thereby improving the antibacterial and mildew-proof effect of the antibacterial and mildew-proof plastic, reducing the yellowing of the antibacterial and mildew-proof plastic, and improving the light transmittance of the antibacterial and mildew-proof plastic.

[0030] (2) The aerogel-type antibacterial and antifungal agent disclosed in the present invention can achieve excellent antibacterial and antifungal effects with a small amount of addition. DETAILED DESCRIPTION

[0031] In order to facilitate understanding of the present disclosure, the present disclosure will be described more fully below. However, the present disclosure can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present disclosure more thorough and comprehensive.

[0032] As used herein:

[0033] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0034] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0035] When amount, concentration or other value or parameter is represented by range, preferred range or a series of upper preferred value and lower preferred value, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when disclosing range "1-5", described range should be interpreted as including range "1-4", "1-3", "1-2", "1-2 and 4-5", "1-3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the range is intended to include its end value and all integers and fractions within the range.

[0036] In these examples, parts and percentages are by mass unless otherwise indicated.

[0037] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0038] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0039] In a first aspect, the present disclosure provides an aerogel-type antibacterial and antifungal agent, comprising the following components in parts by weight: 15-30 parts of zirconium dioxide aerogel, 10-20 parts of antibacterial and antifungal agent, and 0.1-0.5 parts of coating agent;

[0040] Among them, the antibacterial and antifungal agent is at least three of polyhexamethylene biguanide, benzalkonium chloride, benzalkonium bromide, chlorphenesin, cetylpyridinium chloride, cetrimide bromide, benzethonium chloride, chlorhexidine gluconate, and dimethyl ammonium chloride; and the coating agent is hydrophilic wax powder.

[0041] In the aerogel-type antibacterial and mildew-proof agent disclosed in the present invention, zirconium dioxide aerogel is used as a carrier, and the zirconium dioxide aerogel has a porous structure, so that the antibacterial and mildew-proof agent can enter the pores of the zirconium dioxide aerogel, and the coating agent is wrapped on the surface of the zirconium dioxide aerogel and the mildew-proof agent to form a protective film. During the high-temperature processing of the aerogel-type antibacterial and mildew-proof agent and the matrix resin, the zirconium dioxide aerogel and the coating agent melt, absorb the heat on the surface of the antibacterial and mildew-proof agent, make the temperature near the antibacterial and mildew-proof agent lower than the boiling point of the antibacterial and mildew-proof agent, inhibit the decomposition of the mildew-proof agent and improve the high temperature resistance of the mildew-proof agent, improve the mildew-proof effect and light transmittance of the mildew-proof plastic, and reduce the yellowing of the mildew-proof plastic.

[0042] For example, in different embodiments, the weight proportion of the zirconium dioxide aerogel may be, but is not limited to, 15 parts, 17 parts, 19 parts, 21 parts, 23 parts, 25 parts, 28 parts, or 30 parts.

[0043] For example, in different embodiments, the weight proportion of the mildew inhibitor may be, but is not limited to, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts.

[0044] For example, in different embodiments, the weight portion of the coating agent may be, but is not limited to, 0.1 part, 0.2 part, 0.3 part, 0.4 part, or 0.5 part.

[0045] In some embodiments, the zirconium dioxide aerogel has an average porosity of 80-99.8%, an average pore size of 10-40 nm, and an average particle size of 100-150 nm.

[0046] For example, in different embodiments, the porosity of the zirconium dioxide aerogel may be 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96%, 98%, 99.8%;

[0047] The pore size may be, but is not limited to, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm;

[0048] The average particle size may be, but is not limited to, 100 nm, 105 nm, 110 nm, 115 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, 150 nm.

[0049] In the present disclosure, the zirconium dioxide aerogel within the above performance parameter range can better reduce the yellowing effect of the mildew-proof plastic, and increase the mildew-proof effect and light transmittance of the mildew-proof plastic.

[0050] In some embodiments, the average particle size of the hydrophilic wax powder is 100-150 nm.

[0051] For example, in different embodiments, the average particle size of the hydrophilic wax powder can be 100 nm, 105 nm, 110 nm, 115 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, or 150 nm.

[0052] The hydrophilic wax powder with the above average particle size disclosed in the present invention can make the aerogel type antibacterial and mildew-proof agent more evenly distributed in the mildew-proof plastic, which is beneficial to improve the antibacterial and mildew-proof effect and light transmittance of the antibacterial and mildew-proof plastic, and reduce the yellowing of the antibacterial and mildew-proof plastic.

[0053] Specifically, the present invention obtains hydrophilic wax powders with different average particle sizes by ball milling and crushing.

[0054] Those skilled in the art can select appropriate ball milling parameters and pulverization parameters according to actual needs, as long as the hydrophilic wax powder with an average particle size of 100-150 nm can be obtained.

[0055] In a second aspect, a method for preparing the aerogel-type antibacterial and antifungal agent is provided, comprising the following steps:

[0056] After the zirconium dioxide aerogel and the antibacterial and mildew-proof agent aqueous solution are uniformly mixed, a coating agent is added to carry out a first reaction, and the obtained product is dried to obtain an aerogel type antibacterial and mildew-proof agent; wherein the pH value of the antibacterial and mildew-proof agent aqueous solution is 5-7.

[0057] For example, in different embodiments, the pH value of the aqueous solution of the antibacterial and mildew preventer can be, but is not limited to, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, 6.8, or 7.

[0058] The present invention increases the antibacterial and mildew-proof effect and light transmittance of the aerogel-type antibacterial and mildew-proof agent and reduces the yellowing of the antibacterial and mildew-proof plastic by adjusting the pH of the antibacterial and mildew-proof agent aqueous solution. If the pH of the antibacterial and mildew-proof agent aqueous solution is too high or too low, the antibacterial and mildew-proof effect and light transmittance of the aerogel-type antibacterial and mildew-proof agent will deteriorate, and the yellowing of the antibacterial and mildew-proof plastic will increase.

[0059] Specifically, the method for preparing the antibacterial and mildew-proofing agent aqueous solution is as follows: the antibacterial and mildew-proofing agent and water are mixed evenly, a pH adjuster is added, and the mixture is stirred evenly to obtain the antibacterial and mildew-proofing agent aqueous solution with a pH value of 5-7.

[0060] Specifically, the pH adjuster is an acid or base known to those skilled in the art. The type and amount of the pH adjuster are not particularly limited in the present disclosure, as long as the pH value of the mildewcide aqueous solution can be 5-7.

[0061] For example, the acid may be one of hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, acetic acid, and citric acid;

[0062] The alkali may be one of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium carbonate.

[0063] Specifically, the test method for hydrophilic wax powder is: add wax powder to water, stir for 5 minutes, and then observe the situation of wax powder in water; if wax powder is evenly dispersed in water, then the wax powder is hydrophilic wax powder; if wax powder floats on the water surface, then the wax powder is hydrophobic wax powder.

[0064] In some embodiments, based on 100 parts by weight of the antibacterial and mildew-proofing agent aqueous solution, the amount of the antibacterial and mildew-proofing agent is 10-20 parts by weight.

[0065] For example, in different embodiments, based on 100 parts by weight of the antibacterial and mildew-proofing agent aqueous solution, the weight parts of the antibacterial and mildew-proofing agent may be, but are not limited to, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, or 20 parts.

[0066] In some embodiments, the temperature of the first reaction is 50-70°C and the time is 30-40 min;

[0067] As in different embodiments, the temperature of the first reaction can be but is not limited to 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, 62°C, 64°C, 66°C, 68°C, 70°C; the time can be but is not limited to 30 min, 32 min, 34 min, 36 min, 38 min, 40 min.

[0068] The present invention can uniformly mix the zirconium dioxide aerogel and the aqueous solution of the mildew inhibitor by methods known in the art, such as stirring, ultrasound, ball milling, and the like.

[0069] In order to improve the mixing uniformity of zirconium dioxide aerogel and the aqueous solution of antibacterial and mildew-proof agent, the present invention selects an ultrasonic method to evenly mix the zirconium dioxide aerogel and the aqueous solution of antibacterial and mildew-proof agent. Ultrasound can make the antibacterial and mildew-proof agent enter the pores of zirconium dioxide aerogel and distribute evenly, which is beneficial to improving the distribution uniformity of aerogel-type antibacterial and mildew-proof agent in antibacterial and mildew-proof plastic.

[0070] In some embodiments, the ultrasound has a power of 480-800 W and a duration of 15-25 min.

[0071] For example, in different embodiments, the power of the ultrasound can be 480 W, 500 W, 550 W, 600 W, 650 W, 700 W, 750 W, or 800 W; the time can be, but is not limited to, 15 min, 17 min, 19 min, 21 min, 23 min, or 25 min.

[0072] Under the above-mentioned ultrasonic conditions, the antibacterial and mildew-proof agent can be quickly distributed in the zirconium dioxide aerogel. If the ultrasonic time is too short, the content of the antibacterial and mildew-proof agent entering the pore size of the zirconium dioxide aerogel is small, which reduces the antibacterial and mildew-proof effect and light transmittance of the antibacterial and mildew-proof plastic, and increases yellowing.

[0073] In some embodiments, the method for preparing the zirconium dioxide aerogel comprises the following steps:

[0074] Dissolving the zirconium source in the template aqueous solution, then adding the acidifier, and stirring evenly to obtain a first solution;

[0075] adding an acid binding agent to the first solution for neutralization reaction to obtain a zirconium salt sol;

[0076] The zirconium salt sol is subjected to a second reaction and dried to obtain zirconium dioxide aerogel.

[0077] The present invention prepares zirconium dioxide aerogel by a template method, which can improve the porosity of the zirconium dioxide aerogel and increase the loading amount of the antibacterial and mildew-proof agent.

[0078] In some embodiments, the zirconium source is at least one of zirconium oxide, zirconium nitrate, zirconium oxynitrate, zirconium oxychloride, zirconium sulfate, zirconium oxysulfate, and zirconium acetate.

[0079] In some embodiments, the template is a polyether polyol. As an example of a polyether polyol, polyether polyol F127 can be cited.

[0080] In some embodiments, the acid binding agent is at least one of propylene oxide, urea, and ammonia water.

[0081] In some embodiments, the acid regulator is at least one of hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, acetic acid, and citric acid.

[0082] In some embodiments, based on 100 parts by weight of the zirconium salt sol, the zirconium source is 1-3 parts by weight, and the template is 3-6 parts by weight;

[0083] For example, in different embodiments, the weight proportion of the zirconium source can be, but is not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts; the weight proportion of the template can be, but is not limited to, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, or 6 parts.

[0084] In some embodiments, the molar ratio of hydrogen ions in the acid binding agent and the acid regulating agent is 2-20; for example, in different embodiments, the molar ratio of hydrogen ions in the acid binding agent and the acid regulating agent can be but is not limited to 2, 4, 6, 8, 10, 12, 14, 16, 18, 20.

[0085] In some embodiments, the mass ratio of the antibacterial and mildew-proofing agent aqueous solution to the coating agent is 1000:1-5; for example, in different embodiments, the mass ratio of the antibacterial and mildew-proofing agent aqueous solution to the coating agent can be but is not limited to 1000:1, 1000:2, 1000:3, 1000:4, 1000:5.

[0086] The present invention adjusts various parameters in the preparation process of zirconium dioxide aerogel so that the average porosity of zirconium dioxide aerogel is 92%, the average pore diameter is 30nm, and the average particle diameter is 130nm.

[0087] In some embodiments, the temperature of the second reaction is 60-80° C., and the time is 4-12 hours.

[0088] For example, in different embodiments, the temperature of the second reaction may be, but is not limited to, 60°C, 65°C, 70°C, 75°C, or 80°C; and the reaction time may be, but is not limited to, 4h, 6h, 8h, 10h, or 12h.

[0089] In the present disclosure, the temperature of the second reaction will significantly affect the porosity, pore size and average particle size of zirconium dioxide. If the temperature is too low, the porosity and pore size will become smaller, affecting the entry of antibacterial and mildew-proof agent molecules into the aerogel, thereby causing the antibacterial and mildew-proof effect of the prepared antibacterial and mildew-proof agent to fail to meet the requirements. If the temperature is too high, the reaction will be more violent, causing the particle size of the aerogel to be larger, thereby reducing the dispersibility of the prepared aerogel-type antibacterial and mildew-proof agent in plastic products, affecting the appearance of the final product.

[0090] In a third aspect, provided is the use of the aerogel-type antibacterial and mildew-proofing agent or the aerogel-type antibacterial and mildew-proofing agent prepared by the preparation method of the aerogel-type antibacterial and mildew-proofing agent in plastics.

[0091] In a fourth aspect, an antibacterial and mildew-proof plastic is provided, wherein the antibacterial and mildew-proof plastic comprises the aerogel-type antibacterial and mildew-proof agent or an aerogel-type antibacterial and mildew-proof agent prepared by the preparation method of the aerogel-type antibacterial and mildew-proof agent.

[0092] In some embodiments, based on the mass of the antibacterial and mildew-proof plastic being 100%, the mass of the aerogel-type antibacterial and mildew-proof agent is 0.2-0.5%; for example, it may be, but is not limited to, 0.2%, 0.3%, 0.4%, or 0.5%.

[0093] The present invention achieves the antibacterial and mildew-proof effect by adding a small amount of antibacterial and mildew-proof composition to the antibacterial and mildew-proof plastic, while reducing the yellowing of the antibacterial and mildew-proof plastic. If the amount of the aerogel-type antibacterial and mildew-proof agent added is less than 0.2%, the antibacterial and mildew-proof effect of the antibacterial and mildew-proof plastic will decrease; if the amount of the aerogel-type antibacterial and mildew-proof agent added is greater than 0.5%, the aerogel-type antibacterial and mildew-proof agent is unevenly dispersed in the plastic, resulting in a decrease in the light transmittance of the antibacterial and mildew-proof plastic and increased yellowing.

[0094] In some embodiments, the antibacterial and mildew-proof plastic further comprises a base resin, such as polyethylene or polypropylene.

[0095] In addition to the base resin, the antibacterial and mildew-proof plastic may also contain various other functional additives commonly used in plastics, such as antioxidants, light stabilizers, flame retardants, glass fibers, toughening agents, compatibilizers, pigments, coupling agents, dispersants, etc. The types and contents of the above additives can be conventionally selected in the art, which are known to those skilled in the art and will not be described in detail here.

[0096] The present invention can prepare antibacterial and mildew-proof plastics by methods known in the art, such as melt extrusion. The melt extrusion can be carried out by a twin-screw or single-screw extruder, and the temperature of the melt extrusion is 190-230° C. The specific operation process is well known to those skilled in the art.

[0097] The average particle size of each component in the present disclosure is obtained by testing with a particle size analyzer.

[0098] The preferred embodiments of the present invention will be described in more detail below. In the following examples and comparative examples, parts refer to parts by weight.

[0099] Zirconium dioxide aerogel A is homemade, and its preparation method is as follows:

[0100] Add 2 parts of polyether polyol F127 to 50 parts of water and stir evenly to obtain a template aqueous solution;

[0101] Add 1 part of zirconium oxychloride to the template aqueous solution, stir evenly, then add acetic acid, stir evenly, to obtain a first solution with a pH of 4;

[0102] Add 0.002 parts of propylene oxide to the first solution to obtain a second solution, and stir the solution at 50° C. until the pH of the second solution reaches 7 to obtain a zirconium salt sol;

[0103] The zirconium salt sol was reacted at 80°C for 6 hours, dried and crushed to obtain zirconium dioxide aerogel; the obtained zirconium dioxide aerogel had a porosity of 92%, a pore size of 32nm, and a particle size of 132nm;

[0104] Zirconium dioxide aerogel B is homemade, and its preparation method is as follows:

[0105] Add 2 parts of polyether polyol F127 to 50 parts of water and stir evenly to obtain a template aqueous solution;

[0106] Add 1 part of zirconium oxychloride to the template aqueous solution, stir evenly, then add acetic acid, stir evenly, to obtain a first solution with a pH of 4.5;

[0107] Add 0.002 parts of propylene oxide to the first solution to obtain a second solution, and stir the solution at 50° C. until the pH of the second solution reaches 7 to obtain a zirconium salt sol;

[0108] The zirconium salt sol was reacted at 80°C for 6 hours, dried and crushed to obtain zirconium dioxide aerogel; the obtained zirconium dioxide aerogel had an average porosity of 93%, an average pore size of 29 nm, and an average particle size of 125 nm;

[0109] Zirconium dioxide aerogel C is homemade, and its preparation method is as follows:

[0110] Add 2 parts of polyether polyol F127 to 50 parts of water and stir evenly to obtain a template aqueous solution;

[0111] Add 1 part of zirconium oxychloride to the template aqueous solution, stir evenly, then add acetic acid, stir evenly, to obtain a first solution with a pH of 5;

[0112] Add 0.0002 parts of propylene oxide to the first solution to obtain a second solution, and stir the solution at 50° C. until the pH of the second solution reaches 7 to obtain a zirconium salt sol;

[0113] The zirconium salt sol was reacted at 80°C for 6 hours, dried and crushed to obtain zirconium dioxide aerogel; the obtained zirconium dioxide aerogel had an average porosity of 95%, an average pore size of 33 nm, and an average particle size of 114 nm;

[0114] Coating agent A: micronized polyhexene wax, obtained by crushing and screening to obtain coating agent A with a particle size of 125 nm, LS9005, Kunshan Loris Polymer Materials Co., Ltd.;

[0115] Coating agent B: tetrafluoro-modified polyethylene wax powder, obtained by crushing and screening to obtain coating agent B with a particle size of 125 nm, LS9010, Kunshan Loris Polymer Materials Co., Ltd.

[0116] Examples and Comparative Examples

[0117] An aerogel-type antibacterial and antifungal agent comprises the following components, measured by weight: zirconium dioxide aerogel, an antibacterial and antifungal agent, and a coating agent, wherein the specific content of each component is shown in Table 1 below.

[0118] The preparation method of the mildew-proof composition is as follows:

[0119] S1: adding an antibacterial and mildew-proof agent to water, stirring evenly, adding hydrochloric acid or sodium hydroxide, stirring evenly, to obtain an antibacterial and mildew-proof agent aqueous solution, the total mass of the antibacterial and mildew-proof agent aqueous solution is 100 parts;

[0120] S2: adding zirconium dioxide aerogel to the antibacterial and antifungal agent aqueous solution, and ultrasonicating at a power of 600 W for 20 min to obtain an aerogel aqueous solution;

[0121] S3: adding a coating agent to the aerogel aqueous solution at a temperature of 70°C and a stirring speed of 600 r / min, reacting for 30 minutes, and drying and crushing the obtained product to obtain an aerogel type antibacterial and mildew preventer; the particle size range of the obtained aerogel type antibacterial and mildew preventer is 120-170 nm.

[0122] Table 1

[0123]

[0124] Comparative Example 11

[0125] A mildew-proof composition. The preparation method of the mildew-proof composition in this comparative example is different from that in Example 1 only in that the temperature in step S3 is 45° C., and the other components, amounts, steps and parameters are the same as those in Example 1.

[0126] Comparative Example 12

[0127] A mildew-proof composition. The preparation method of the mildew-proof composition in this comparative example is different from that in Example 1 only in that the temperature in step S3 is 75° C., and the other components, amounts, steps and parameters are the same as those in Example 1.

[0128] Comparative Example 13

[0129] A mildew-proof composition. The preparation method of the mildew-proof composition in this comparative example is different from that in Example 1 only in that the ultrasonication time in step S3 is 10 minutes, and the other components, amounts, steps and parameters are the same as those in Example 1.

[0130] Performance Testing

[0131] The mildew-proof compositions and polypropylene obtained in the above embodiments and comparative examples were uniformly mixed. The weights of the mildew-proof compositions and polypropylene were shown in Table 2 below. The mixtures were added into a twin-screw extruder preheated to 200° C. for melt extrusion, sheeting and cutting to obtain mildew-proof plastic sheets with a size of 40 mm*40 mm 3 mm. The performance of the mildew-proof plastic sheets was tested.

[0132] The test method is as follows:

[0133] (1) Antibacterial test: GB31402-2015 "Test method for antibacterial performance of plastic surface" was used for testing: the killing effect on bacteria was observed for 3 days;

[0134] Bacteria used for detection: Staphylococcus aureus, Escherichia coli.

[0135] (2) Anti-mildew test: Test in accordance with GBT24128-2018 "Evaluation of the anti-mildew effect of anti-mildew agents for plastics": observe the growth of mold after 21 days of cultivation;

[0136] Level 0: No growth, i.e. no growth was observed under a microscope (magnification 50 times);

[0137] Level 1: Initial growth, i.e. growth is visible to the naked eye, but the growth covers ≤ 10% of the area;

[0138] Grade 2: obvious growth and spore production, i.e., growth covering > 10% of the area;

[0139] Detection bacteria: a mixture of Aspergillus niger, Trichoderma longibrachiatum, Paecilomyces variotii, Chaetomium globosum and Penicillium funiculosum.

[0140] (3) Yellowing degree: Use a colorimeter to test the b value of the square plastic plate, and evaluate the degree of yellowing of the material based on the size of the b value;

[0141] (4) Light transmittance: The light transmittance percentage of a square plastic plate is tested at 950nm in a colorimeter.

[0142] The test results are shown in Table 2 below.

[0143] Table 2

[0144]

[0145] From the experimental data in Table 2, it can be seen that when the aerogel-type antibacterial and mildew-proof agent of the present invention is added to the antibacterial and mildew-proof plastic in an amount of 0.2%, the antibacterial and mildew-proof plastic can achieve a mildew-proof effect of level 0 and a bacteria killing effect of 99.99%, and the color and transparency of the antibacterial and mildew-proof plastic change little, indicating that the aerogel-type antibacterial and mildew-proof agent of the present invention has excellent and broad-spectrum antibacterial and mildew-proof effects and will not affect the original appearance and performance of the plastic.

[0146] By comparing Examples 1-3 and Comparative Examples 1-2, it can be seen that when the pH of the aqueous solution of the antibacterial and mildew-proof agent is in the range of 5-7, the mildew-proof grade of the obtained antibacterial and mildew-proof plastic is 0, the yellowing degree is 2.32-2.47, and the light transmittance is 77-78%, indicating that only when the pH of the aqueous solution of the antibacterial and mildew-proof agent is in the range of 5-7, can a mildew-proof and mildew-proof plastic with high light transmittance and low yellowing degree be obtained.

[0147] By comparing Example 2, Examples 8-10 and Comparative Examples 3-4, it can be seen that when the weight portion of zirconium dioxide aerogel is 20-25 parts, the mildew resistance grade of the obtained antibacterial and mildew-proof plastic is 0, the yellowing degree is 2.32-2.35, and the light transmittance is 77-78%, indicating that when the weight portion of zirconium dioxide aerogel is 20-25 parts, the mildew-proof and antibacterial plastic has the advantages of mildew resistance, high light transmittance, and low yellowing degree.

[0148] By comparing Example 2, Examples 11-14 and Comparative Examples 5-6, it can be seen that when the weight portion of the coating agent is 0.2-0.4 parts, the mildew resistance grade of the obtained antibacterial and mildew proof plastic is level 0, the yellowing degree is 2.32-2.43, and the light transmittance is 74-78%, indicating that when the weight portion of the coating agent is 0.2-0.4 parts, the obtained mildew proof and antibacterial plastic has high mildew resistance effect and light transmittance, and low yellowing degree.

[0149] By comparing Example 2 with Comparative Examples 7-8, it can be seen that when zirconium dioxide aerogel or coating agent is lacking, the mildew proof effect and light transmittance of the obtained antibacterial and mildew proof plastic are significantly reduced, and yellowing increases.

[0150] By comparing Example 2 and Comparative Example 10, it can be seen that when the type of antibacterial and mildew-proof agent is reduced by one, the mildew-proof effect and light transmittance of the antibacterial and mildew-proof plastic will decrease, and the yellowing will increase. Only when three different antibacterial and mildew-proof agents interact with each other can the mildew-proof effect and light transmittance of the antibacterial and mildew-proof plastic be improved and the degree of yellowing be reduced.

[0151] By comparing Example 2 with Comparative Examples 11-13, it can be seen that only when the aerogel-type antibacterial and mildew-proof agent is prepared under specific conditions and applied to antibacterial and mildew-proof plastics, can the mildew-proof effect and light transmittance of the antibacterial and mildew-proof plastics be improved and the yellowing degree be reduced.

[0152] Finally, it should be noted that the above embodiments are used to illustrate the technical solution of the present disclosure rather than to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present disclosure can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present disclosure.

Claims

1. An aerogel antibacterial and antifungal agent, characterized in that: The invention comprises the following components in parts by weight: 15-30 parts of zirconium dioxide aerogel, 10-20 parts of antibacterial and mildew-proof agent, and 0.1-0.5 parts of coating agent; The antibacterial and antifungal agent is at least three of polyhexamethylene biguanide, benzalkonium chloride, benzalkonium bromide, chlorphenesin, cetylpyridinium chloride, cetrimide bromide, benzethonium chloride, chlorhexidine gluconate, and didecyl dimethyl ammonium chloride; the coating agent is hydrophilic wax powder; The preparation method of the aerogel type antibacterial and mildew-proof agent comprises the following steps: after uniformly mixing zirconium dioxide aerogel and an antibacterial and mildew-proof agent aqueous solution, adding a coating agent for reaction, and drying the obtained product to obtain the aerogel type antibacterial and mildew-proof agent; wherein the pH value of the antibacterial and mildew-proof agent aqueous solution is 5-7; The reaction temperature is 50-70°C and the reaction time is 30-40min; The uniform mixing method is ultrasound, and the ultrasound time is 15-25 minutes; The preparation method of the zirconium dioxide aerogel comprises the following steps: Dissolving the zirconium source in the template aqueous solution, then adding the acidifier, stirring evenly, to obtain a first solution with a pH value of 4-5; Adding an acid binding agent to the first solution for neutralization reaction to obtain a zirconium salt sol with a pH of 7; The zirconium salt sol is heated for reaction and dried to obtain zirconium dioxide aerogel; The template agent is polyether polyol; The acid binding agent is at least one of propylene oxide, urea and ammonia water; Based on 100 parts by weight of the zirconium salt sol, the zirconium source is 1-3 parts by weight, and the template is 3-6 parts by weight; The heating reaction temperature is 60-80°C and the time is 4-12h.

2. The aerogel antibacterial and antifungal agent according to claim 1, characterized in that: The zirconium dioxide aerogel has an average porosity of 80-99.8%, an average pore diameter of 10-40 nm, and an average particle diameter of 100-150 nm.

3. The aerogel antibacterial and antifungal agent according to claim 1, characterized in that: The average particle size of the hydrophilic wax powder is 100-150 nm.

4. The method for preparing the aerogel antibacterial and antifungal agent according to any one of claims 1 to 3, characterized in that: The following steps are involved: The zirconium dioxide aerogel and the antibacterial and mildew-proof agent aqueous solution are uniformly mixed, a coating agent is added for reaction, and the obtained product is dried to obtain an aerogel-type antibacterial and mildew-proof agent; wherein the pH value of the antibacterial and mildew-proof agent aqueous solution is 5-7; The reaction temperature is 50-70°C and the reaction time is 30-40min; The uniform mixing method is ultrasound, and the ultrasound time is 15-25 minutes; The preparation method of the zirconium dioxide aerogel comprises the following steps: Dissolving the zirconium source in the template aqueous solution, then adding the acidifier, stirring evenly, to obtain a first solution with a pH value of 4-5; Adding an acid binding agent to the first solution for neutralization reaction to obtain a zirconium salt sol with a pH of 7; The zirconium salt sol is heated for reaction and dried to obtain zirconium dioxide aerogel; The template agent is polyether polyol; The acid binding agent is at least one of propylene oxide, urea and ammonia water; Based on 100 parts by weight of the zirconium salt sol, the zirconium source is 1-3 parts by weight, and the template is 3-6 parts by weight; The heating reaction temperature is 60-80°C and the time is 4-12h.

5. The method for preparing the aerogel antibacterial and mildew-proof agent according to claim 4, characterized in that: Based on 100 parts by weight of the antibacterial and mildew-proofing agent aqueous solution, the antibacterial and mildew-proofing agent accounts for 10-20 parts by weight.

6. The method for preparing the aerogel antibacterial and antifungal agent according to claim 4, characterized in that: The zirconium source is at least one of zirconium oxide, zirconium nitrate, zirconium oxynitrate, zirconium oxychloride, zirconium sulfate, zirconium oxysulfate, and zirconium acetate; The acid regulator is at least one of hydrochloric acid, sulfuric acid, oxalic acid, nitric acid, acetic acid and citric acid.

7. Use of the aerogel antibacterial and mildewproofing agent prepared by the aerogel antibacterial and mildewproofing agent according to any one of claims 1 to 3 or the method for preparing the aerogel antibacterial and mildewproofing agent according to any one of claims 4 to 6 in the preparation of plastics. 8.An antibacterial and mildew-proof plastic, characterized in that: The antibacterial and mildew-proof plastic includes the aerogel-type antibacterial and mildew-proof agent as claimed in any one of claims 1 to 3 or the aerogel-type antibacterial and mildew-proof agent prepared by the preparation method of the aerogel-type antibacterial and mildew-proof agent as claimed in any one of claims 4 to 6.

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