Toothpaste capable of stably inhibiting bacteria for long time

Abstract

The invention discloses long-time stable bacteriostatic toothpaste, the toothpaste comprises a bacteriostatic agent, the bacteriostatic agent is composed of zinc oxide, nano-silver particles and povidone iodine, the zinc oxide is porous zinc oxide, the povidone iodine is distributed in internal holes of the porous zinc oxide, and the nano-silver particles are distributed on the surfaces of the porous zinc oxide particles. According to the toothpaste disclosed by the invention, the zinc oxide, the nano-silver particles and the povidone iodine are ingeniously combined together, so that a composite bacteriostatic agent which has multiple antibacterial mechanisms, a long-acting antibacterial effect, high safety, excellent physical properties and multiple oral health effects is formed. The antibacterial effect of the toothpaste is improved, the action time of the antibacterial components is prolonged, the safety and environmental protection property of the product are ensured, and the toothpaste is expected to be widely applied to more oral care products and has certain economic value.

Description

Technical Field

[0001] The present invention relates to the field of oral cleaning products, in particular to the field of toothpaste, and in particular to a toothpaste with long-term stable antibacterial properties. Background Art

[0002] Oral health is an important component of overall human health, and toothpaste, as a primary tool for daily oral care, plays an important role. As people's attention to oral health continues to increase, traditional cleaning toothpaste can no longer meet the needs of modern consumers. The oral cavity is one of the main pathways for pathogens to enter the human body, and the use of toothpaste with antibacterial effects can not only prevent oral diseases but also reduce the risk of pathogen transmission through the oral cavity. Therefore, toothpaste with antibacterial effects has gradually become a popular product on the market, especially in the context of frequent global public health events and increased antibacterial awareness. People have begun to pay more attention to personal hygiene and protection, especially oral hygiene, and the demand for antibacterial toothpaste has become more urgent.

[0003] Antibacterial toothpaste mainly produces antibacterial effects by adding antibacterial agents to toothpaste. Common antibacterial toothpastes on the market mainly contain active antibacterial ingredients such as chlorhexidine, triclosan, and povidone-iodine (PVP-I). For example, CN114469777A discloses a toothpaste for improving periodontitis. The toothpaste is composed of the following components by weight: 700-800 parts of silicon dioxide (ML-520A), 100-180 parts of silicon dioxide (ML-520B), 500-700 parts of sorbitol aqueous solution, 4-6 parts of xanthan gum, 1-5 parts of chlorhexidine acetate, 1-3 parts of sodium saccharin, 5-10 parts of sodium monofluorophosphate, 1-10 parts of sodium laurate sulfate aqueous solution, and 1-2 parts of ethyl hydroxybenzoate. The raw material cost is low, the preparation process is simple, and the resulting toothpaste has no toxic effects on the human body and is safe and reliable to use. It is mild and non-irritating, is not easy to damage tooth enamel, can kill bacteria and inhibit bacteria, and has a particularly good improvement effect on periodontitis, bleeding gums, swollen and painful gums, and bad breath. However, long-term use of chlorhexidine may cause tooth discoloration and taste changes, and the above toothpaste is not suitable for daily use. CN113797152A discloses an oral antibacterial toothpaste composed of the following raw materials: 0.05-0.3 parts of triclosan, 1-3 parts of sorbitol, 1-3 parts of menthol, 3-5 parts of hydrated silica, 3-5 parts of plant polypeptides, 1-3 parts of sodium phytate, 5-8 parts of biological lysozyme, 5-8 parts of menthol, 5-8 parts of honeysuckle extract, 3-5 parts of glycerin, 1-3 parts of bletilla striata extract, 1-3 parts of liquorice extract, 3-5 parts of Lactobacillus paracasei, 8-10 parts of orange peel powder, 8-10 parts of sodium lauryl sulfate, 1-3 parts of lactoferrin, 1-2 parts of essence, and 10-15 parts of purified water. The toothpaste can inhibit harmful bacteria, maintain beneficial bacteria, has an antibacterial and refreshing effect, regulates the balance of oral flora, maintains oral autoimmunity, and protects oral health. Although triclosan has a good antibacterial effect, its safety is controversial. Long-term use may have adverse effects on the environment and human health, such as endocrine disruption and drug resistance. CN117618330A discloses a toothpaste that improves dispersibility, stability, and iodine delivery efficiency. The antibacterial composition includes povidone iodine and poloxamer. Poloxamer can reduce interfacial tension and promote the opening of polyvinyl pyrrolidone chains to disperse in water. It also includes sodium hyaluronate with a molecular weight greater than 600,000, which can increase the adhesion of effective iodine, improve the utilization rate of effective iodine, and at the same time avoid the attenuation of effective iodine caused by poloxamer, thereby improving the inhibition of oral microorganisms. Although povidone iodine is a commonly used broad-spectrum antibacterial agent that can effectively kill a variety of bacteria, viruses, and fungi, and has high safety. However, povidone iodine has poor stability and is easy to react with other substances in the toothpaste, affecting the overall lifespan.In addition, there are other bacteriostatic agents, such as zinc compounds (such as zinc oxide, zinc chloride, zinc sulfate), chitosan, nano-silver, hydrogen peroxide, etc., but the antibacterial effect of zinc compounds and chitosan is relatively weak, nano-silver requires a higher toothpaste system and is prone to blackening; the antibacterial effect of hydrogen peroxide is relatively short, and high-concentration hydrogen peroxide can irritate the oral mucosa, causing discomfort. Therefore, in order to improve the antibacterial effect of toothpaste, multiple antibacterial components are often used in combination, but the composition of toothpaste itself is relatively complex, and multiple components are prone to reaction with each other or the antibacterial agent is prone to reaction with other components in the toothpaste, affecting the antibacterial effect or the stability of the toothpaste.

[0004] At the same time, the oral health status and needs of different groups of people are different, for example, children, the elderly, pregnant women and other special groups have different requirements for toothpaste. How to develop a safe toothpaste with long-term stable antibacterial effect and individualization suitable for different groups of people is one of the future development directions. SUMMARY

[0005] In order to solve the defects in the prior art, the present application provides a toothpaste with long-term stable antibacterial effect, which comprises a bacteriostatic agent composed of zinc oxide, nano-silver particles and povidone iodine, wherein the zinc oxide is porous zinc oxide, the povidone iodine is distributed in the internal pores of the porous zinc oxide, and the nano-silver particles are distributed on the surface of the porous zinc oxide particles. The structural design of the above-mentioned bacteriostatic agent enables the toothpaste to provide multiple antibacterial mechanisms. The porous zinc oxide itself has certain antibacterial performance and can interfere with the metabolic process of bacteria by releasing zinc ions to inhibit their growth and reproduction; nano-silver has a strong inhibitory effect on a variety of bacteria, fungi and viruses, especially on drug-resistant bacteria; povidone iodine is a broad-spectrum antibacterial agent that can release free iodine to destroy bacterial cell membranes and protein structures, leading to bacterial death, and has an inhibitory effect on a variety of bacteria, viruses, fungi and protozoa. By combining these three components together, the toothpaste can effectively inhibit harmful bacteria in the oral cavity and prevent oral diseases such as gingivitis and periodontitis; in addition, the povidone iodine is distributed in the internal pores of the porous zinc oxide, and when the toothpaste is used, the povidone iodine will gradually be released from the pores, prolonging the duration of its antibacterial effect. The zinc ions provided by the zinc oxide can further enhance the antibacterial performance of the povidone iodine, forming a synergistic effect. The nano-silver particles are distributed on the surface of the porous zinc oxide particles, forming a "double-layer protection" system. The nano-silver particles can remain stable in the oral environment and will not be easily diluted or washed away by saliva or other substances, providing long-term antibacterial effect. The synergistic use of the three can provide a wider antibacterial spectrum and stronger antibacterial effect. Compared with traditional toothpaste, the toothpaste in the present application can significantly prolong the action time of the antibacterial components and provide all-weather protection.

[0006] In order to achieve the above-mentioned purpose of the invention, the present application provides a toothpaste with long-term stable antibacterial effect, which contains an antibacterial agent, which is composed of zinc oxide, nano-silver particles and povidone iodine. The zinc oxide in the antibacterial agent is porous zinc oxide, the povidone iodine is distributed in the pores inside the porous zinc oxide, and the nano-silver particles are distributed on the surface of the porous zinc oxide particles.

[0007] Furthermore, the mass ratio of zinc oxide, nanosilver particles, and povidone-iodine in the antibacterial agent is 10-30:0.05-0.5:0.5-1. Preferably, the mass ratio of zinc oxide, nanosilver particles, and povidone-iodine in the antibacterial agent is 20-30:0.1-0.5:0.5-1; further preferably, the mass ratio of zinc oxide, nanosilver particles, and povidone-iodine in the antibacterial agent is 30:0.2:1. The nanosilver has a particle size of 20-200 nm.

[0008] Furthermore, the preparation method of the antibacterial agent in the toothpaste is as follows:

[0009] (1) Preparation of porous zinc oxide particles: Slowly drip a 0.5-1 mol / L potassium hydroxide solution into a 0.1-0.5 mol / L zinc acetate solution at 50-80°C under stirring, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and the molar ratio of zinc ions to hydroxide ions is maintained at 1:3. Stir until the particles are uniformly dispersed; place the dispersed system in a reactor and react at 100-150°C for 1-5 hours. After the reaction is completed, centrifuge, wash, and dry to obtain porous zinc oxide. The porous zinc oxide prepared by this method has a large specific surface area and abundant surface pores.

[0010] (2) Preparing a porous zinc oxide-silver nanoparticle composite material: Weighing the porous zinc oxide and silver nitrate prepared in step (1) in a ratio of zinc oxide to elemental silver of 10-30:0.05-0.5; adding the porous zinc oxide to a silver nitrate aqueous solution with a concentration of 0.05-0.1M, and magnetically stirring for 1-5 hours under light-proof conditions to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; continuing the magnetic stirring, irradiating the mixed solution with an ultraviolet lamp for 2-5 hours, centrifuging, washing with deionized water, and drying to obtain a porous zinc oxide-silver nanoparticle composite material; the power of the ultraviolet lamp is 50-100W.

[0011] (3) Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: Weigh the porous zinc oxide-silver nanoparticles and povidone iodine powder obtained in step (2) at a zinc oxide:povidone iodine mass ratio of 10-30:0.5-1, mix the two and put them into a ball mill for ball milling, so that the povidone iodine powder is completely dispersed in the pores inside the porous zinc oxide, and then take it out.

[0012] Furthermore, the ball milling time in step (3) is 5 to 10 hours, the average particle size of the particles after ball milling is 5 to 30 μm, and the particle distribution is relatively uniform.

[0013] Furthermore, the toothpaste further comprises an abrasive, a moisturizing agent, a thickener, a foaming agent, an essence and water. The abrasive is hydrated silica, and the particle size of the abrasive is 5 to 20 μm. Apart from this, no other abrasives or other additives are required to be introduced into the toothpaste.

[0014] Furthermore, the moisturizing agent is at least one of polyethylene glycol, glycerin, sorbitol and propylene glycol; the thickener is at least one of hydroxyethyl cellulose, xanthan gum and carrageenan; the foaming agent is at least one of sodium lauryl sulfate, sodium lauryl sulfate and cocamidopropyl betaine; and the flavor is at least one of sodium saccharin, stevia and sucralose.

[0015] Furthermore, the toothpaste is composed of an abrasive, an antibacterial agent, a moisturizing agent, a thickener, a foaming agent, a flavor and water. The amount of each component is as follows by weight: 15-25% abrasive, 20-40% antibacterial agent, 10-30% moisturizing agent, 1-5% thickener, 0.5-1% foaming agent, 0.05-0.5% flavor, and the balance is water.

[0016] Furthermore, the toothpaste is composed of an abrasive, an antibacterial agent, a moisturizing agent, a thickener, a foaming agent, a flavor and water. By weight percentage, the toothpaste is composed of 20% abrasive, 30% antibacterial agent, 15% moisturizing agent, 2% thickener, 1% foaming agent, 0.5% flavor, and the balance is water. The antibacterial agent is prepared from porous zinc oxide, nanosilver particles and povidone iodine in a mass ratio of 30:0.5:1.

[0017] The present application also provides a method for preparing a long-lasting stable antibacterial toothpaste, comprising the following steps:

[0018] 1. Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite materials: slowly dripping a potassium hydroxide solution with a concentration of 0.5-1 mol / L into a zinc acetate solution with a concentration of 0.1-0.5 mol / L under stirring at 50-80°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 100-150°C for 1-5 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; according to the mass ratio of zinc oxide to elemental silver of 10-30:0.05-0.5 The obtained porous zinc oxide and silver nitrate are weighed; the porous zinc oxide is added to a silver nitrate aqueous solution with a concentration of 0.05 to 0.1 M, and magnetically stirred for 1 to 5 hours in a dark environment to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring is continued, and the mixed solution is irradiated with an ultraviolet lamp for 2 to 5 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; porous zinc oxide-silver nanoparticles and povidone iodine powder are weighed in a zinc oxide to povidone iodine mass ratio of 10 to 30:0.5 to 1, the two are mixed, and then ball milled in a ball mill to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide, and then taken out;

[0019] 2. Weigh the porous zinc oxide-silver nanoparticles-povidone iodine composite material, abrasive, humectant, thickener, foaming agent, flavor and water in proportion, mix the abrasive, humectant, thickener, foaming agent, flavor and water, then add the porous zinc oxide-silver nanoparticles-povidone iodine and continue stirring until the paste is evenly dispersed to obtain a uniform paste. Vacuum degas the paste and then can it.

[0020] Compared with the prior art, the technical solution of this application has the following beneficial effects:

[0021] 1. The present application designs a new antibacterial agent structure. The composite antibacterial agent enables toothpaste to provide multiple antibacterial mechanisms. Porous zinc oxide itself has certain antibacterial properties and can interfere with the metabolic process of bacteria by releasing zinc ions, inhibiting their growth and reproduction. Nanosilver has a strong inhibitory effect on a variety of bacteria, fungi and viruses, especially against drug-resistant bacteria. Povidone iodine is a broad-spectrum antibacterial agent that can release free iodine, destroy bacterial cell membranes and protein structures, causing bacterial death, and has an inhibitory effect on a variety of bacteria, viruses, fungi and protozoa. By combining these three ingredients, toothpaste can effectively inhibit harmful bacteria in the mouth and prevent oral diseases such as gingivitis and periodontitis. In addition, povidone iodine is distributed in the internal pores of porous zinc oxide. When the toothpaste is used, povidone iodine will gradually be released from the pores, prolonging the duration of its antibacterial effect. The zinc ions provided by zinc oxide can further enhance the antibacterial properties of povidone iodine, forming a synergistic effect. Nanosilver particles are distributed on the surface of porous zinc oxide particles, forming a "double-layer protection" system. Nanosilver particles can remain stable in the oral environment and will not be easily diluted or washed away by saliva or other substances. Nanosilver can continue to work for a long time and provide a long-lasting antibacterial effect. When used, nanosilver can directly act on bacteria on the surface of the oral cavity, while zinc oxide can inhibit the growth of deep-seated bacteria by releasing zinc ions. The synergistic use of the three can provide a wider antibacterial spectrum and a stronger antibacterial effect. Compared with traditional toothpaste, the toothpaste in this application can significantly prolong the action time of the antibacterial ingredients and provide all-day protection.

[0022] 2. The toothpaste product in this application has good stability and will not stratify and settle after long-term use. The raw materials of the product are green and safe, and the toothpaste product has good safety. Zinc oxide has good biocompatibility and safety. It will not be absorbed in the human body and is suitable for long-term use. In addition, zinc oxide also has the effect of promoting the remineralization of tooth enamel, which helps to enhance the hardness and anti-caries ability of teeth to a certain extent; nanosilver particles are distributed on the surface of porous zinc oxide particles, and the interaction between the two is strong, which reduces the direct contact between nanosilver and oral mucosa and reduces potential health risks. By combining zinc oxide, nanosilver and povidone iodine, a multifunctional composite material is formed, which reduces the dependence on other chemical additives. This design not only simplifies the formula, but also improves the safety and environmental protection of the product.

[0023] 3. The porous zinc oxide in the product not only has antibacterial properties but also has a certain abrasive effect, helping to remove stains and plaque from the tooth surface. Compared to traditional abrasives, porous zinc oxide has finer particles and moderate friction, effectively cleaning teeth without damaging tooth enamel, which can reduce the amount of abrasive used in toothpaste. By distributing povidone-iodine and nanosilver within and on the surface of the porous zinc oxide, a stable composite structure is formed. This structure prevents interactions between the different components, ensuring the stability of the toothpaste during storage and use, and extending the product's shelf life. Porous zinc oxide has a large specific surface area, which can absorb odor molecules in the mouth and reduce the occurrence of bad breath. At the same time, the antibacterial effects of nanosilver and povidone-iodine can inhibit the bacteria that cause bad breath, fundamentally solving the problem of bad breath. DETAILED DESCRIPTION

[0024] To make the technical problems solved by the present invention, the technical solutions adopted, and the technical effects achieved more clearly, the technical solutions of the embodiments of the present invention will be further described in detail below. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0025] It should be noted that references to "embodiments" herein mean that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of such phrases in various locations in the specification does not necessarily refer to the same embodiment, nor does it necessarily refer to independent or alternative embodiments that are mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0026] The experimental methods in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are commercially available unless otherwise specified.

[0027] The toothpastes of each embodiment and comparative example were tested as follows:

[0028] 1. Stability test: Take an appropriate amount of toothpaste sample, put it into a plastic centrifuge tube, place it in a refrigerator at -8℃±1℃, take it out after 8 hours, and randomly put it into a constant temperature incubator at 60℃±1℃. Take it out after 20 hours, return to room temperature, open the lid, and check the state of the paste.

[0029] 2. Toothpaste antibacterial test: Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were used as test strains. E. coli and Staphylococcus aureus were cultured in LB medium, while Candida albicans was cultured in YPD medium. During the test, a single colony was picked and placed in 2 mL of liquid culture medium and cultured overnight. The bacterial concentration was adjusted to 0D using the corresponding culture medium. 600 About 0.5, and then diluted 100 times with culture medium as bacterial suspension for later use; weigh 1g of different toothpastes, add them to the bacterial suspension (containing 2 to 3 glass beads for dispersing toothpaste), shake to dissolve the toothpaste, and let it stand for 3 minutes; dilute with sterile saline in a gradient manner, count the diluted samples by the spot seeding method, and calculate the bactericidal rate; shake to dissolve the toothpaste in the same way and let it stand for 24 hours; dilute with sterile saline in a gradient manner, count the diluted samples by the spot seeding method, and calculate the bactericidal rate.

[0030] Example 1

[0031] A method for preparing an antibacterial toothpaste comprises the following steps:

[0032] 1. Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: slowly dripping a potassium hydroxide solution with a concentration of 0.5 mol / L into a zinc acetate solution with a concentration of 0.1 mol / L under stirring at 50°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 100°C for 1 hour. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; weighing the obtained porous zinc oxide and silver nitrate according to a mass ratio of zinc oxide to elemental silver of 10:0.05; The porous zinc oxide was added to a 0.05M silver nitrate aqueous solution and magnetically stirred for 1 hour in the dark to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring was continued, and the mixed solution was irradiated with a 50W ultraviolet lamp for 5 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; porous zinc oxide-silver nanoparticles and povidone iodine powder were weighed at a zinc oxide:povidone iodine mass ratio of 10:0.5, and the two were mixed and placed in a ball mill for 5 hours to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide. The particles were taken out and the average particle size after ball milling was measured to be 30μm;

[0033] 2. Weigh hydrated silica, porous zinc oxide-silver nanoparticles-povidone iodine composite material, polyethylene glycol, xanthan gum, sodium lauryl sulfate, sodium saccharin and water in a mass ratio of 15:20:10:1:0.5:0.05:53.45, mix the hydrated silica, polyethylene glycol, xanthan gum, sodium lauryl sulfate, sodium saccharin and water and stir evenly, then add porous zinc oxide-silver nanoparticles-povidone iodine and continue stirring until uniform dispersion to obtain a uniform paste, vacuum degas the paste and can it to obtain the toothpaste.

[0034] The toothpaste product was tested and found to have a stable shape, no stratification or water precipitation, suitable consistency, fine paste and good stability. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923 and Candida albicans as test strains were 100%, 100% and 100% respectively, and the 24-hour sterilization rates were 100%, 100% and 100% respectively. It can be seen that the toothpaste has good bactericidal and inhibitory ability against the above pathogens, and the toothpaste meets the relevant requirements of GB / T8372-2017.

[0035] Example 2

[0036] A method for preparing an antibacterial toothpaste comprises the following steps:

[0037] 1. Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: slowly dripping a potassium hydroxide solution with a concentration of 1 mol / L into a zinc acetate solution with a concentration of 0.5 mol / L under stirring at 80°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 150°C for 5 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; weighing the obtained porous zinc oxide and silver nitrate in a ratio of zinc oxide to elemental silver of 30:0.5; Zinc oxide was added to a 0.1M silver nitrate aqueous solution and magnetically stirred for 5 hours in the dark to allow silver ions to adsorb on the surface of the porous zinc oxide to obtain a mixed solution. The magnetic stirring was continued and the mixed solution was irradiated with a 100W ultraviolet lamp for 2 hours. The mixed solution was centrifuged and washed with deionized water and dried to obtain a porous zinc oxide-silver nanoparticle composite material. Porous zinc oxide-silver nanoparticles and povidone iodine powder were weighed in a zinc oxide:povidone iodine mass ratio of 30:1, the two were mixed, and then ball milled in a ball mill for 10 hours to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide. The particles were taken out and measured to have an average particle size of 5 μm after ball milling.

[0038] 2. Weigh hydrated silica, porous zinc oxide-silver nanoparticles-povidone iodine composite material, glycerol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water in a mass ratio of 20:40:30:5:1:0.5:3.5, mix the hydrated silica, glycerol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water, stir evenly, then add porous zinc oxide-silver nanoparticles-povidone iodine and continue stirring until uniform dispersion to obtain a uniform paste, vacuum degas the paste and can it to obtain the toothpaste.

[0039] The toothpaste product was tested and found to have a stable shape, no stratification or water precipitation, suitable consistency, fine paste and good stability. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923 and Candida albicans as test strains were 100%, 100% and 100% respectively, and the 24-hour sterilization rates were 100%, 100% and 100% respectively. It can be seen that the toothpaste has good bactericidal and inhibitory ability against the above pathogens, and the toothpaste meets the relevant requirements of GB / T8372-2017.

[0040] Example 3

[0041] A method for preparing an antibacterial toothpaste comprises the following steps:

[0042] 1. Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: slowly dripping a potassium hydroxide solution with a concentration of 1 mol / L into a zinc acetate solution with a concentration of 0.3 mol / L under stirring at 70°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 120°C for 3 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; weighing the obtained porous zinc oxide and silver nitrate in a ratio of zinc oxide to elemental silver of 20:0.1; The porous zinc oxide was added to a 0.1M silver nitrate aqueous solution and magnetically stirred for 3 hours in the dark to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring was continued, and the mixed solution was irradiated with a 70W ultraviolet lamp for 3 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; porous zinc oxide-silver nanoparticles and povidone iodine powder were weighed at a zinc oxide:povidone iodine mass ratio of 20:1, the two were mixed, and then placed in a ball mill for 8 hours to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide. The particles were taken out and the average particle size after ball milling was measured to be 12 μm;

[0043] 2. Weigh hydrated silica, porous zinc oxide-silver nanoparticles-povidone iodine composite material, sorbitol, carrageenan, cocamidopropyl betaine, sucralose and water in a mass ratio of 25:30:20:1:1:0.5:22.5; mix sorbitol, carrageenan, cocamidopropyl betaine, sucralose and water, add hydrated silica and stir evenly; then add porous zinc oxide-silver nanoparticles-povidone iodine and continue stirring until uniform dispersion to obtain a uniform paste; vacuum degas the paste and can it to obtain the toothpaste.

[0044] The toothpaste product was tested and found to have a stable shape, no stratification or water precipitation, suitable consistency, fine paste and good stability. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923 and Candida albicans as test strains were 100%, 100% and 100% respectively, and the 24-hour sterilization rates were 100%, 100% and 100% respectively. It can be seen that the toothpaste has good bactericidal and inhibitory ability against the above pathogens, and the toothpaste meets the relevant requirements of GB / T8372-2017.

[0045] Example 4

[0046] A method for preparing an antibacterial toothpaste comprises the following steps:

[0047] 1. Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: slowly dripping a potassium hydroxide solution with a concentration of 0.5 mol / L into a zinc acetate solution with a concentration of 0.1 mol / L under stirring at 80°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 140°C for 2 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; weighing the obtained porous zinc oxide and silver nitrate in a ratio of zinc oxide to elemental silver of 20:0.2; Zinc oxide was added to a 0.05M silver nitrate aqueous solution and magnetically stirred for 4 hours in the dark to allow silver ions to adsorb on the surface of the porous zinc oxide to obtain a mixed solution. The magnetic stirring was continued and the mixed solution was irradiated with a 50W ultraviolet lamp for 5 hours. The mixed solution was centrifuged and washed with deionized water and dried to obtain a porous zinc oxide-silver nanoparticle composite material. Porous zinc oxide-silver nanoparticles and povidone iodine powder were weighed in a zinc oxide:povidone iodine mass ratio of 20:0.5, mixed, and then ball-milled in a ball mill for 5 hours to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide. The particles were taken out and measured to have an average particle size of 24 μm after ball milling.

[0048] 2. Take hydrated silica, porous zinc oxide-silver nanoparticle-povidone iodine composite material, propylene glycol, hydroxyethyl cellulose, sodium dodecyl sulfate, stevia and water according to the mass ratio of 20:30:15:2:1:0.5:31.5, mix and stir the hydrated silica, propylene glycol, hydroxyethyl cellulose, sodium dodecyl sulfate, stevia and water until uniform, then add the porous zinc oxide-silver nanoparticle-povidone iodine and continue stirring until uniformly dispersed to obtain a uniform paste, vacuum degas the paste, then fill the jar to obtain the toothpaste.

[0049] The toothpaste product is detected, and the detection shows that the toothpaste has stable shape, no delamination or water separation, appropriate consistency, fine paste body, good stability, 3min sterilization rate of 100%, 100%, 100% for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, Candida albicans as test strains, and 24h sterilization rate of 100%, 100%, 100%, which shows that the toothpaste has good bacteriostatic ability for the above-mentioned pathogenic bacteria, and the toothpaste meets the relevant requirements of GB / T8372-2017.

[0050] Comparative Example 1

[0051] A preparation method of an antibacterial toothpaste, comprising the following steps:

[0052] 1. Prepare porous zinc oxide: slowly drop a potassium hydroxide solution with a concentration of 0.5mol / L into a zinc acetate solution with a concentration of 0.1mol / L under stirring at 80℃, the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, the molar ratio of zinc ions to hydroxide ions is maintained at 1:3, and stirring is performed until uniform dispersion; place the dispersion system in a reaction kettle, react at 140℃ for 2h, after the reaction is completed, centrifugal separation, cleaning and drying are performed to obtain porous zinc oxide; put it into a ball mill for 5h, take it out, and measure the average particle size after ball milling, which is 2μm;

[0053] 2. Take hydrated silica, porous zinc oxide, propylene glycol, hydroxyethyl cellulose, sodium dodecyl sulfate, stevia and water according to the mass ratio of 20:30:15:2:1:0.5:31.5, mix and stir the hydrated silica, propylene glycol, hydroxyethyl cellulose, sodium dodecyl sulfate, stevia and water until uniform, then add the porous zinc oxide and continue stirring until uniformly dispersed to obtain a uniform paste, vacuum degas the paste, then fill the jar to obtain the toothpaste.

[0054] The toothpaste product was tested and found to have a stable shape, no stratification or water precipitation, and an appropriate consistency. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans were 82%, 41%, and 8%, respectively, and the 24-hour sterilization rates were 57%, 22%, and 1%, respectively. This shows that the toothpaste has a certain inhibitory ability against the above-mentioned pathogens, but its long-term stability is poor.

[0055] Comparative Example 2

[0056] A method for preparing toothpaste comprises the following steps:

[0057] 1. Preparation of porous zinc oxide-povidone iodine composite material: slowly dripping a potassium hydroxide solution with a concentration of 0.5 mol / L into a zinc acetate solution with a concentration of 0.1 mol / L under stirring at 80°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniformly dispersed; placing the dispersed system in a reactor and reacting at 140°C for 2 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; porous zinc oxide and povidone iodine powder are weighed according to a zinc oxide:povidone iodine mass ratio of 20:0.5, the two are mixed, and then placed in a ball mill for 5 hours to allow the povidone iodine powder to be completely dispersed into the pores inside the porous zinc oxide. The particles are taken out and the average particle size after ball milling is measured to be 18 μm;

[0058] 2. Weigh hydrated silica, porous zinc oxide-povidone iodine particles, propylene glycol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water in the mass ratio of 20:30:15:2:1:0.5:31.5, mix the hydrated silica, propylene glycol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water, then add the porous zinc oxide-povidone iodine particles and continue stirring until they are evenly dispersed to obtain a uniform paste. Vacuum degas the paste and then can it to obtain the toothpaste.

[0059] The toothpaste product was tested and found to have a stable shape, without stratification or water precipitation. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans as test strains were 95%, 82%, and 92%, respectively, and the 24-hour sterilization rates were 86%, 73%, and 88%, respectively. This shows that the toothpaste has a certain inhibitory ability against the above-mentioned pathogens. Although the sterilization rate decreased after 24 hours, it still has a good antibacterial effect.

[0060] Comparative Example 3

[0061] A method for preparing toothpaste comprises the following steps:

[0062] 1. Preparation of porous zinc oxide-silver nanoparticles: slowly dripping a 0.5 mol / L potassium hydroxide solution into a 0.1 mol / L zinc acetate solution stirred at 80°C, wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until uniform dispersion; placing the dispersed system in a reactor and reacting at 140°C for 2 hours. After the reaction is completed, centrifugation, washing, and drying are performed to obtain porous zinc oxide; according to the mass ratio of zinc oxide to elemental silver, The porous zinc oxide and silver nitrate obtained are weighed in a ratio of 20:0.2; the porous zinc oxide is added to a 0.05M silver nitrate aqueous solution, and magnetically stirred for 4 hours in a dark environment to allow silver ions to adsorb on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring is continued, and the mixed solution is irradiated with a 50W ultraviolet lamp for 5 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; the above material is placed in a ball mill and milled for 5 hours, and then taken out. The average particle size of the particles after ball milling is measured to be 17 μm;

[0063] 2. Weigh hydrated silica, porous zinc oxide-silver nanoparticles, povidone iodine, propylene glycol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water in a mass ratio of 20:30:0.8:15:2:1:0.5:31.5, mix the hydrated silica, povidone iodine, propylene glycol, hydroxyethyl cellulose, sodium lauryl sulfate, stevioside and water, stir well, add porous zinc oxide-silver nanoparticles and continue stirring until uniform dispersion to obtain a uniform paste, vacuum degas the paste and can it to obtain the toothpaste.

[0064] The toothpaste product was tested, and the results showed that a small amount of light yellow precipitate appeared in the toothpaste, and there was slight water precipitation in the paste. The 3-minute sterilization rates for Escherichia coli ATCC 8739, Staphylococcus aureus ATCC 25923, and Candida albicans as test strains were 91%, 77%, and 89%, respectively, and the 24-hour sterilization rates were 68%, 52%, and 73%, respectively. It can be seen that the toothpaste has poor stability, and the 24-hour sterilization rate for the above-mentioned pathogens decreased significantly, indicating poor stability of the toothpaste.

[0065] From the test results of the above embodiments and comparative examples, it can be seen that the toothpaste prepared in the embodiments of the present invention can significantly improve the antibacterial and anti-inflammatory ability of the toothpaste, has a stable and long-term high-efficiency antibacterial effect, has strong antibacterial ability and good stability.

[0066] The above is a detailed introduction to a toothpaste with long-term stable antibacterial properties. The above content is a further detailed description of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, without departing from the concept of the present invention, its structural form can be flexible and changeable, and a series of products can be derived. Just making a few simple deductions or replacements should be considered to fall within the scope of patent protection of the present invention as determined by the submitted claims.

Claims

1. A toothpaste with long-term stable antibacterial effect, comprising an antibacterial agent consisting of zinc oxide, nanosilver particles and povidone iodine, characterized in that: The zinc oxide is porous zinc oxide, the povidone iodine is distributed in the internal pores of the porous zinc oxide, and the nano silver particles are distributed on the surface of the porous zinc oxide particles.

2. The long-term stable antibacterial toothpaste according to claim 1, characterized in that The mass ratio of zinc oxide, nano silver particles and povidone iodine in the antibacterial agent is 10-30:0.05-0.5:0.5-1.

3. The long-term stable antibacterial toothpaste according to claim 1, characterized in that The preparation method of the antibacterial agent is as follows: (1) Preparing porous zinc oxide particles: slowly dripping a potassium hydroxide solution with a concentration of 0.5 to 1 mol / L into a zinc acetate solution with a concentration of 0.1 to 0.5 mol / L under stirring at 50 to 80° C., wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water with a volume ratio of 1:1, maintaining a molar ratio of zinc ions to hydroxide ions of 1:3, and stirring until the particles are uniformly dispersed; placing the dispersed system in a reactor, reacting at 100 to 150° C. for 1 to 5 hours, and after the reaction is completed, centrifuging, washing, and drying to obtain porous zinc oxide; (2) preparing a porous zinc oxide-silver nanoparticle composite material: weighing the porous zinc oxide and silver nitrate prepared in step (1) in a ratio of zinc oxide to elemental silver of 10-30:0.05-0.5; The porous zinc oxide is added to a silver nitrate aqueous solution having a concentration of 0.05 to 0.1 M, and magnetically stirred for 1 to 5 hours in a dark environment to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring is continued, and the mixed solution is irradiated with an ultraviolet lamp for 2 to 5 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; (3) Preparation of porous zinc oxide-silver nanoparticles-povidone iodine composite material: Weigh the porous zinc oxide-silver nanoparticles and povidone iodine powder obtained in step (2) at a zinc oxide:povidone iodine mass ratio of 10-30:0.5-1, mix the two and put them into a ball mill for ball milling, so that the povidone iodine powder is completely dispersed in the pores inside the porous zinc oxide, and then take it out.

4. The long-term stable antibacterial toothpaste according to claim 3, characterized in that The ball milling time is 5 to 10 hours, and the average particle size of the particles after ball milling is 5 to 30 μm.

5. The long-term stable antibacterial toothpaste according to claim 1, characterized in that The toothpaste further comprises an abrasive, a moisturizing agent, a thickener, a foaming agent, essence and water.

6. The long-term stable antibacterial toothpaste according to claim 5, characterized in that The friction agent is hydrated silica, and the particle size of the friction agent is 5 to 20 μm.

7. The long-term stable antibacterial toothpaste according to claim 5, characterized in that The moisturizing agent is at least one of polyethylene glycol, glycerin, sorbitol and propylene glycol; the thickener is at least one of hydroxyethyl cellulose, xanthan gum and carrageenan; the foaming agent is at least one of sodium lauryl sulfate, sodium lauryl sulfate and cocamidopropyl betaine; and the flavor is at least one of sodium saccharin, stevia and sucralose.

8. The long-term stable antibacterial toothpaste according to claim 1, characterized in that The toothpaste consists of an abrasive, an antibacterial agent, a moisturizing agent, a thickener, a foaming agent, an essence and water. The dosage of each component is as follows by weight: 15-25% of abrasive, 20-40% of antibacterial agent, 10-30% of moisturizing agent, 1-5% of thickener, 0.5-1% of foaming agent, 0.05-0.5% of essence, and the balance is water.

9. The long-term stable antibacterial toothpaste according to claim 8, wherein the toothpaste is composed of 20% abrasive, 30% antibacterial, 15% moisturizer, 2% thickener, 1% foaming agent, 0.5% flavor, and the balance is water, characterized in that: The antibacterial agent is prepared from porous zinc oxide, nano silver particles and povidone iodine in a mass ratio of 30:0.5:

1.

10. A method for preparing a toothpaste with long-term stable antibacterial properties according to any one of claims 1 to 9, characterized in that: The steps include:

1. Prepare a porous zinc oxide-silver nanoparticle-povidone iodine composite material: slowly drip a potassium hydroxide solution with a concentration of 0.5 to 1 mol / L into a zinc acetate solution with a concentration of 0.1 to 0.5 mol / L under stirring at 50 to 80° C., wherein the solvent of the zinc acetate solution is a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and the molar ratio of zinc ions to hydroxide ions is maintained at 1:3, and stir until uniformly dispersed; place the dispersed system in a reactor and react at 100 to 150° C. for 1 to 5 hours. After the reaction is completed, centrifuge, wash, and dry to obtain porous zinc oxide; weigh the obtained porous zinc oxide and silver nitrate according to a ratio of zinc oxide to elemental silver of 10 to 30:0.05 to 0.5 by mass; The porous zinc oxide is added to a silver nitrate aqueous solution having a concentration of 0.05 to 0.1 M, and magnetically stirred for 1 to 5 hours in a dark environment to allow silver ions to be adsorbed on the surface of the porous zinc oxide to obtain a mixed solution; the magnetic stirring is continued, and the mixed solution is irradiated with an ultraviolet lamp for 2 to 5 hours, centrifuged, washed with deionized water, and dried to obtain a porous zinc oxide-silver nanoparticle composite material; porous zinc oxide-silver nanoparticles and povidone iodine powder are weighed in a zinc oxide to povidone iodine mass ratio of 10 to 30:0.5 to 1, the two are mixed, and then ball milled in a ball mill to allow the povidone iodine powder to be completely dispersed in the pores inside the porous zinc oxide, and then taken out; 2. Weigh the porous zinc oxide-silver nanoparticles-povidone iodine composite material, abrasive, humectant, thickener, foaming agent, flavor and water in proportion, mix the abrasive, humectant, thickener, foaming agent, flavor and water, then add the porous zinc oxide-silver nanoparticles-povidone iodine and continue stirring until the paste is evenly dispersed to obtain a uniform paste. Vacuum degas the paste and then can it.